JP2013542219A - Nitrogen-containing heterocyclic carbene complex, its production and use thereof - Google Patents

Abstract

［式中、ｎは0または1であり、
Mは金属原子含有基であり、
R¹は、水素とアルキル、シクロアルキル、ヘテロシクロアルキル、アリール、ヘタリールから選ばれ、
R²は、水素とアルキル、シクロアルキル、ヘテロシクロアルキル、アリール、ヘタリールから選ばれ［但し、R¹とR²は両方とも水素であることはない］、
R³とR⁴、R⁵、R⁶、R⁷、R⁸は、請求項1の定義どおりである］。
また、本発明は、その製造方法、及びそのC-C結合、C-O結合、C-N結合またはC-H結合の形成反応に用いられる触媒としての使用方法に関する。The present invention relates to nitrogen-containing heterocyclic carbene complexes of formula I.
[Chemical 1]

[Wherein n is 0 or 1;
M is a metal atom-containing group,
R ¹ is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
R ² is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl [provided that R ¹ and R ² are not both hydrogen],
R ³ and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are as defined in claim 1].
The present invention also relates to a method for producing the same and a method for using the same as a catalyst used in a reaction for forming a CC bond, a CO bond, a CN bond or a CH bond.

Description

  The present invention relates to a nitrogen-containing heterocyclic carbene complex, a method for producing the same, and a method for using the same as a catalyst.

  In 1968, H.W. Wanzlick and K. Ofele independently reported the first direct synthesis of metal complexes with nitrogen-containing heterocyclic carbene (NHC) as a ligand. At that time, none would have been able to predict the role these ligands would play in decades. In particular, NHC complexes of Pd (II) are widely used in recent organic chemistry and organometallic chemistry. Compared with other ligands such as phosphane, NHC is superior in terms of thermal stability, low toxicity, insensitivity to oxygen, etc., so NHC complexes can be combined with Heck coupling, Sonogami, Suzuki-Miyaura, Still, Hartwig-Buchwald. It can be used in many different coupling reactions such as coupling. In particular, the Suzuki-Miyaura reaction currently plays an important role because of the stability, availability and low toxicity of the boronic acid used.

  In addition to use in catalysts, NHC complexes are also useful in many other fields such as medical applications, nanoparticles, supramolecular chemistry, self-assembly, photochemistry, liquid crystals, polymerization, and electron active materials.

  Although these special ligands have many advantages, there are still difficulties in the synthesis of saturated NHC complexes. AJ Arduengo, R. Krafczyk, and R. Schmutzler, in Tetrahedron 1999, 55, 14523-14534, synthesized imidazolidene, imidazolinylidene and imidazolidine starting from glyoxal and via the corresponding diimine and diamine dihydrochloride. It is described. These diamine dihydrochlorides are then converted to the corresponding imidazolinium salts by reaction with orthoformate as the C1 building block. Reduction of the imidazolinium salt with lithium aluminum hydride yields imidazolidine, which is deprotonated with potassium hydride to produce the corresponding imidazoline-2-ylidene. However, this method does not synthesize particularly asymmetrically substituted NHC.

  B. A. Bhanu Prasad and S. R. Gilbertson describe a one-pot synthesis of asymmetric NHC ligands from N- (2-iodoethyl) arylamine salts in Org. Lett. 2009, 11, 3710-3713.

  This route is limited to the synthesis of NHCs with specific substituents. It is known to use isonitrile metal complexes for the synthesis of acyclic or cyclic carbenes.

  K. Bartel and WP Fehlhammer described in Angew. Chem. Int. Ed. 1974, 13, 599-600 oxazolidinylidene of Pd, Pt, and Au by the reaction of 2- and 3-hydroxyalkyl isocyanides with metal compounds. Describes the synthesis of complexes and perhydrooxazinylidene complexes.

  U. Plaia and WP Fehlhammer describe the preparation of hexakis (oxazolidin-2-ylidene) cobalt (III) and rhodium (III) in J. Am. Chem. Soc. 1985, 107, 2171-2172. .

  M. Tamm and F. E. Hahn describe the synthesis of carbene complexes from coordinated β-functional phenyl isocyanides in Coord. Chem. Rev. 1999, 182, 175-209.

  RA Michelin and L. Zanotto, D. Braga, P. Sabatino and RJ Angelici, in Inorg. Chem. 1988, 27, 85-92, developed a cyclic aminooxycarbene by cyclization of isocyanide complex and 2-bromoethanol. Describes Pt (II) complexes.

  I. Yu and CJ Wallis, BO Patrick, PL Diaconescu, P. Mehrkhodavandi, doi: 10.1021 / om100841j, using a primary amine and strain-activated iron-isonitrile / phosphane chelate, a slightly unrelated reaction Has been reported.

  RA Michelin and L. Zanotto, D. Braga, P. Sabatino, RJ Angelici, Inorg. Chem. 1988, 27, 93-99, Pd (of cyclic diaminocarbene by cyclization reaction of isocyanide complex and 2-bromoethylamine. The synthesis of II) and Pt (II) complexes is described.

  R. A. Michelin and A. J. L. Pombeiro and M. F. C. Guedes da Silva report in Coord. Chem. Rev. 2001, 218, 75-112 an aminocarbene complex by nucleophilic addition to an isocyanide ligand.

  The methods described in the last three documents give NHCs in which one nitrogen atom is unsubstituted and the other nitrogen atom can only be attached to an alkyl substituent. The synthesis of free NHC often requires a long organic synthesis step, and it is often difficult to combine the NHC ligand thus synthesized with a metal, requiring other synthesis steps.

A. J. Arduengo, R. Krafczyk, R. Schmutzler; Tetrahedron 1999, 55, 14523-14534. B. A. Bhanu Prasad, S. R. Gilbertson; Org. Lett. 2009, 11, 3710-3713. K. Bartel, W. P. Fehlhammer; Angew. Chem. Int. Ed. 1974, 13, 599-600. U. Plaia, W. P. Fehlhammer; J. Am. Chem. Soc. 1985, 107, 2171-2172. M. Tamm, F. E. Hahn; Coord. Chem. Rev. 1999, 182, 175-209. R. A. Michelin, L. Zanotto, D. Braga, P. Sabatino and R. J. Angelici; Inorg. Chem. 1988, 27, 85-92. I. Yu, C. J. Wallis, B. O. Patrick, P. L. Diaconescu, P. Mehrkhodavandi; doi: 10.1021 / om100841j. R. A. Michelin, L. Zanotto, D. Braga, P. Sabatino, R. J. Angelici; Inorg. Chem. 1988, 27, 93-99. R. A. Michelin, A. J. L. Pombeiro and M. F. C. Guedes da Silva; Coord. Chem. Rev. 2001, 218, 75-112.

  There is still a need for an effective method that can produce N, N′-disubstituted NHC complexes, particularly asymmetrically disubstituted NHC complexes. These metal NHC complexes must be stable to air and easy to handle.

Surprisingly, it has been found that this object is achieved by reaction of substituted ω-haloalkylammonium salts or ω- (alkoxycarbonyl) alkylammonium salts with readily available isonitrile complexes.
The present invention relates to compounds of general formula (I):

(Where
n is 0 or 1,
M is a metal atom-containing group,
R ¹ is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
R ² is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl (provided that R ¹ and R ² are not hydrogen at the same time),
R ³ and R ⁴ are independently hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (di-cycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, aryl-thio, Selected from (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
R ³ and R ⁴ together with the carbon atom bonded to them are C═O,
R ³ is an OR ^3a group,
if n = 0, R ⁴ and R ⁷ are the same bond as the double bond between carbon atoms with R ⁴ and R ⁷ respectively, or
When n = 1, R ⁴ and R ⁵ are the same bond as the double bond between carbon atoms having R ⁴ and R ⁵ respectively,
R ^3a is a group bonded to oxygen via a carbon atom, a silicon atom, a sulfur atom, a phosphorus atom, a boron atom or a titanium atom,
R ⁵ and R ⁶ , R ⁷ , R ⁸ are independently hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy , Cycloalkylthio, (monocycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkyl-thio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, Aryloxy, arylthio, (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
The two groups R ² and R ⁸ are 3-membered to 12-membered unsubstituted or substituted nitrogen heterocycles with the N atom to which R ² is attached, and if necessary independently as ring components, then O and N , NR ^a (R ^a is hydrogen, alkyl, cycloalkyl or aryl), one, two or three other heteroatoms or heteroatom-containing groups selected from S Often,
Or
When n = 0, R ⁴ and R ⁷ may also be the same bond as the double bond between carbon atoms having R ⁴ and R ⁷ ),
a1) Isonitrile complexes of the general formula (II):

(Wherein R ¹ and M have one of the above meanings);
Compounds of general formula (III) or (IIIa):

(Where
n and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ have one of the above meanings,
X ^- is an anion equivalent,
Y is a leaving group, or
When R ³ and R ⁴ are C═O together with the carbon atom attached to it, Y is a group OY ^a (where Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted Or a substituted alkylcarbonyl, or an unsubstituted or substituted arylcarbonyl)
b1) If necessary, when R ³ and R ⁴ together with the carbon atom to which they are attached are C = O, the product obtained in step a1) is treated with compound R ^3a -Z (formula In which Z is a leaving group, and the compound of formula (I) wherein R ³ is an OR ^3a group, and when n = 0, R ⁴ and R ⁷ are R ⁴ and R ⁽ It is the same bond as the double bond between carbon atoms having ⁷ or when n = 1, R ⁴ and R ⁵ are the same bond as the double bond between carbon atoms having R ⁴ and R ⁵ ) Including getting or
a2) Isonitrile complexes of the general formula II:

(Where R ¹ and M have one of the above meanings)
And compounds of general formula (V):

(Where
R ² , R ³ and R ⁸ have one of the above meanings,
R ¹⁰ and R ¹¹ are independently selected from C ₁ -C ₄ -alkyl, or R ¹⁰ and R ¹¹ together are a line optionally substituted with one or more C ₁ -C ₄ -alkyl groups. A C ₂ -C ₄ -alkylene substituent)
Intermediate compound of formula (VI) in reaction with:

を得、また、
b2)式(ＶＩ)の中間体化合物を酸で処理することを含む
(なお、この実施例で得られる化合物(Ｉ)において、nは0であり、R⁴とR⁷はR⁴とR⁷をもつ炭素原子間の二重結合と同じ結合である);
または
a3)一般式ＩＩのイソニトリル錯体：

And also
b2) comprising treating an intermediate compound of formula (VI) with an acid
(In the compound (I) obtained in this example, n is 0, and R ⁴ and R ⁷ are the same bonds as double bonds between carbon atoms having R ⁴ and R ⁷ );
Or
a3) Isonitrile complexes of the general formula II:

(Wherein R ¹ and M have one of the above meanings) and compounds of general formula (IIIb) or (IIIc):

(Where
R ² and R ⁴ , R ⁷ and R ⁸ have one of the above meanings.
X ^- is an anion equivalent;
EWG (C (O) R ¹⁴ , C (O) OR ¹⁴ , NO ₂ , S (O) R ¹⁴ or S (O) ₂ R ^{14 where} R ¹⁴ is hydrogen, alkyl, cycloalkyl or aryl Reacting with
(However, in the compound (I) obtained in modification a3), n is 0 and R ³ is CH2-EWG).

  In a first aspect, the present invention provides a compound of general formula (I):

(Where
n is 0 or 1,
M is a metal atom-containing group,
R ¹ is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
R ² is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl (note that R ¹ and R ² are not hydrogen at the same time),
R ³ and R ⁴ are independently hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (di-cycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, aryl-thio, Selected from (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
R ³ and R ⁴ together with the carbon atom bonded to them are C═O,
R ³ is an OR ^3a group,
When n = 0, R ⁴ and R ⁷ are the same bond as a double bond between carbon atoms having R ⁴ and R ⁷ respectively.
Alternatively, R ³ is an OR ^3a group,
When n = 1, R ⁴ and R ⁵ are the same bonds as double bonds between carbon atoms having R ⁴ and R ⁵ respectively.
R ^3a is a group bonded to oxygen via a carbon atom, a silicon atom, a sulfur atom, a phosphorus atom, a boron atom or a titanium atom,
R ⁵ and R ⁶ , R ⁷ , R ⁸ are independently hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy , Cycloalkylthio, (monocycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkyl-thio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, Aryloxy, arylthio, (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
The two groups R ² and R ⁸ are 3-membered to 12-membered unsubstituted or substituted nitrogen heterocycles with the N atom to which R ² is bound, and if necessary independently as ring components, then O and N , NR ^a (R ^a is hydrogen, alkyl, cycloalkyl or aryl), may form one, two or three other heteroatoms or heteroatom-containing groups selected from S )
a1) of the isonitrile complex of the general formula (II)

(Wherein R ¹ and M have one of the above meanings);
Compounds of general formula (III) or (IIIa):

(Where
n and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ have one of the above meanings,
X ^- is an anion equivalent,
Y is a leaving group, or
When R ³ and R ⁴ are C═O together with the carbon atom attached to it, Y is a group OY ^a (where Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted Or a substituted alkylcarbonyl, or an unsubstituted or substituted arylcarbonyl)
b1) If necessary, when R ³ and R ⁴ together with the carbon atom to which they are attached are C = O, the product obtained in step a1) is treated with compound R ^3a -Z (formula In which Z is a leaving group, and the compound of formula (I) wherein R ³ is an OR ^3a group, and when n = 0, R ⁴ and R ⁷ are R ⁴ and R ⁽ It is the same bond as the double bond between carbon atoms having ⁷ or when n = 1, R ⁴ and R ⁵ are the same bond as the double bond between carbon atoms having R ⁴ and R ⁵ ) Providing a method comprising:

In a particular embodiment, the method of the invention is used to form asymmetrically substituted compounds of formula (I). In this embodiment, it is preferred that R ¹ and R ² have different meanings.

  The first variant is a compound of formula (IA-1) or (IA-2):

(Where
M and R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ have the meanings described above and below,
R ³ and R ⁴ are independently hydrogen, in each case unsubstituted or substituted alkyl and alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) ) Amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino)
a1) Isonitrile complexes of the general formula (II):

(Wherein R ¹ and M have ^one of the above or below meanings) and a compound of general formula (III) or (IIIa):

(Where
n and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ have one of the above or the following meanings:
X ^- is an anion equivalent,
Y is a production method including a reaction with a leaving group.

  The second variant is a compound of general formula (I-B.1) or (I-B.2):

(Where
M and R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ have the meanings described above and below),
a1) Isonitrile complexes of the general formula (II):

(Wherein R ¹ and M have ^one of the above or below meanings);
Compounds of general formula (III-B.1), (III-B.1.a), (III-B.2) or (III-B.2.a):

(Where
R ² and R ⁵ , R ⁶ , R ⁷ , R ⁸ have one of the meanings described above or below,
X ^- is an anion equivalent,
Y ^a is a production method including a reaction with unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted arylcarbonyl or unsubstituted or substituted alkylcarbonyl.

  If the keto compounds of the general formula (I-B.1) or (I-B.2) are capable of forming tautomers, these tautomers are also part of the present invention.

  The third variant is a compound of general formula (I-C.1) or (I-C.2):

(Where
M and R ¹ , R ² , R ^3a , R ⁶ , R ⁷ , R ⁸ have the above-mentioned meanings),
a1) Isonitrile complexes of the general formula (II):

(Wherein R ¹ and M have one of the above meanings);
Compounds of general formula (III-C.1), (III-C.1.a), (III-C.2) or (III-C.2.a)

(Where
R ² and R ⁶ , R ⁷ , R ⁸ have one of the above meanings,
X ^- is an anion equivalent,
Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted arylcarbonyl or unsubstituted or substituted alkylcarbonyl)
b1) A production method comprising reacting the product obtained in step a1) with a compound R ^3a -Z (wherein Z is a leaving group) in the presence of a base.

In a second aspect, the present invention relates to a compound of general formula (IE) (compound of formula I, wherein n is 0, R ⁴ and R ⁷ are two carbon atoms between R ⁴ and R ^7). (Same bond as double bond):

(Where
M is a metal atom-containing group,
R ¹ is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl,
R ² is selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl (R ¹ and R ² are not simultaneously hydrogen),
R ³ is hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl) amino, ( (Dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) amino, (diaryl) Amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
Chosen from
R ⁸ is hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl) amino, ( (Dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) amino, (diaryl) Amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
The two groups R ² and R ⁸ together with the N atom to which R ² is attached, optionally independently O and N, NR ^a (where R ^a is hydrogen and alkyl, cycloalkyl or aryl. Forming a 3- to 12-membered unsubstituted or substituted nitrogen heterocycle optionally containing 1, 2 or 3 other heteroatoms or heteroatom-containing groups selected from S as part of the ring A manufacturing method),
a2) Isonitrile complexes of the general formula II:

(Wherein R ¹ and M have one of the above meanings),
Compound of general formula (V):

(Where
R ² , R ³ and R ⁸ have one of the above meanings,
R ¹⁰ and R ¹¹ are independently selected from C ₁ -C ₄ -alkyl, or R ¹⁰ and R ¹¹ together are a line optionally substituted with one or more C ₁ -C ₄ -alkyl groups. A C ₂ -C ₄ -alkylene substituent)
In reaction with
Intermediate compound of formula (VI):

(式中、R¹とR²、R³、R⁸、R¹⁰、R¹¹、Mは上述の通りである)を得ること;
また
b2)式(ＶＩ)の中間体化合物を酸で処理することを含む方法を提供する。

(Wherein R ¹ and R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ , M are as described above);
Also
b2) A method comprising treating an intermediate compound of formula (VI) with an acid is provided.

In a special embodiment, the method of the invention of the second aspect is used for the formation of asymmetrically substituted compounds of formula (IE). In this embodiment, it is preferred that R ¹ and R ² have different meanings.

In a third aspect, the present invention relates to a compound of general formula IF (compound of formula I, wherein n is 0 and R ³ is CH ₂ -EWG):

(Wherein R ¹ and R ² , R ⁴ , R ⁷ , R ⁸ , M, EWG have one of the above-mentioned meanings),
a3) Isonitrile complexes of the general formula II:

(Wherein R ¹ and M have one of the above meanings) and compounds of general formula (IIIb) or (IIIc):

(Where
EWG and R ² , R ⁴ , R ⁷ , R ⁸ have one of the above meanings,
X ^- is an anion equivalent) and provides a method comprising reaction with.

In a special embodiment, the inventive method of the third aspect is used for the formation of asymmetrically substituted compounds of formula (IF). In this embodiment, it is preferred that R ¹ and R ² have different meanings.

  In another aspect, the present invention provides novel compounds of general formula (I).

  In another aspect, the present invention provides a novel compound of general formula (VI).

  In another aspect, the present invention provides a catalyst comprising or consisting of a compound of general formula (I).

  In another aspect, the present invention provides the use of a compound of general formula (I) as or in a catalyst for use in a C—C bond forming reaction, a C—O, C—N, or C—H bond forming reaction.

  In another particular embodiment, the compound of general formula (I) is used in a C—C coupling reaction selected from Suzuki reaction and Heck reaction, Sonogashira reaction, Stille reaction, Hartwig-Buchwald reaction, Kumada reaction.

  In another particular embodiment, compounds of general formula (I) are used for hydrogenation, hydroformylation, hydrosilylation, Hartwig-Buchwald reaction or α-arylation of amides.

  For the purposes of the present invention, “nitrogen-containing heterocyclic carbene (NHC)” refers to a compound that can exist in the form of different resonance structures, eg, having a divalent carbon atom structure or an ylide-type structure.

  Preferred embodiments of the compounds of general formula (I) are those described above and below in formulas (I-A.1) and (I-A.2), (I-B.1), (I-B.2) , (I-C.1) and (I-C.2). Unless otherwise stated, all definitions relating to compounds of general formula (I) are given by formulas (I-A.1) and (I-A.2), (I-B.1), (I-B.2) , (I-C.1), (I-C.2). Preferred embodiments of the compounds of general formula (I) are also the compounds of formulas (IE) and (IF) described above and below. Unless otherwise stated, all definitions relating to compounds of general formula (I) also apply to compounds of formulas (IE) and (IF).

In the present invention, a single bond is used to show the MC _carbene interaction in the compounds of formulas (I) and (VI).

  “Halogen” in each case refers to fluorine, bromine, chlorine or iodine, in particular chlorine, bromine or iodine.

  In the present invention, “unsubstituted or substituted alkyl or alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl) amino, (dicycloalkyl) amino” , Heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) amino, (diaryl) amino, hetaryl, hetaryl `` Reeloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino '' are unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted (monoalkyl) amino, Unsubstituted or placed Substituted (dialkyl) amino, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkoxy, unsubstituted or substituted cycloalkylthio, unsubstituted or substituted (monocycloalkyl) amino, unsubstituted or substituted (di Cycloalkyl) amino, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heterocycloalkoxy, unsubstituted or substituted heterocycloalkylthio, unsubstituted or substituted (monoheterocycloalkyl) amino, unsubstituted or substituted (Diheterocycloalkyl) amino, unsubstituted or substituted aryl, unsubstituted or substituted aryloxy, unsubstituted or substituted arylthio, unsubstituted or substituted (monoaryl) amino, unsubstituted or substituted (diaryl) amino , Unsubstituted or substituted hetaryl, unsubstituted or substituted hetaryloxy, unsubstituted or substituted Tariruchio refers unsubstituted or substituted (Monohetariru) amino, unsubstituted or substituted with (Jihetariru) amino.

In the present invention, “alkyl” refers to a linear or branched alkyl group. Alkyl is preferably C ₁ -C ₃₀ -alkyl, more preferably C ₁ -C ₂₀ -alkyl, most preferably C ₁ -C ₁₂ -alkyl. Examples of alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n -Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl.

“Alkyl” also includes one or more selected from —O— and —S—, NR ^b —, C (═O), S (═O) and / or —S (═O) ₂ — in the carbon chain. Also includes alkyl groups having non-adjacent groups. R ^b is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

The substituted alkyl group may have one or more (eg, 1, 2, 3, 4, 5, 6 or more) substituents depending on the length of the alkyl chain. These are each independently cycloalkyl and heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO ₃ H, sulfonate, sulfamino, sulfamide, amidino, NE ¹ E ² (where E ¹ and E ² are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl) It is preferable. Alkyl cycloalkyl and heterocycloalkyl, aryl, and hetaryl substituents may also be unsubstituted or substituted, and suitable substituents are those described above for these groups.

  Carboxylate and sulfonate refer to derivatives of carboxylic acid functional groups and sulfonic acid functional groups, respectively, in particular metal carboxylate or sulfonate functional groups, carboxylic acid ester or sulfonic acid ester functional groups or carboxamide or sulfonamide functional groups.

  The above definitions for alkyl also apply to alkyl groups in alkoxy, alkylthio (= alkylsulfanyl), monoalkylamino and dialkylamino groups.

  In the present invention, “cycloalkyl” usually means a monocyclic, bicyclic or tricyclic ring having 3 to 20 carbon atoms, preferably 3 to 12, more preferably 5 to 12 carbon atoms. It represents a hydrocarbon group, specifically cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbornyl, bicyclo [2.2.2] octyl or adamantyl.

The substituted cycloalkyl group may have one or more (for example, 1, 2, 3, 4, 5, 6 or more) substituents depending on the size of the ring. These are each independently alkyl and alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkyl Carbonyloxy, carbamoyl, SO ₃ H, sulfonate, sulfamino, sulfamide, amidino, NE ³ E ^{4 where} E ³ and E ⁴ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl Is preferably selected from the group consisting of When substituted, these cycloalkyl groups preferably have one or more (eg, one, two, three, four or five) C ₁ -C ₆ -alkyl groups. Examples of substituted cycloalkyl groups are in particular 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3- and 4-propylcyclohexyl, 2-, 3- and 4-isopropylcyclohexyl, 2-, 3- and 4-butylcyclohexyl, 2-, 3- and 4-sec-butylcyclohexyl, 2-, 3- and 4 -tert-butylcyclohexyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 2-, 3- and 4-propyl¬ cycloheptyl, 2-, 3- and 4 -Isopropylcycloheptyl, 2-, 3- and 4-butylcycloheptyl, 2-, 3- and 4-sec-butylcycloheptyl, 2-, 3- and 4-tert-butylcycloheptyl, 2-, 3- 4-, 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclohexane Chill, 2-, 3-, 4- and 5-propyl cyclooctyl.

  The above definition for cycloalkyl also applies to cycloalkyl groups in cycloalkoxy and cycloalkylthio (= cycloalkylsulfanyl), monocycloalkylamino, dicycloalkylamino.

  In the present invention, “aryl” refers to a monocyclic or polycyclic aromatic hydrocarbon group. Aryl is usually an aromatic group having 6 to 24 carbon atoms, preferably 6 to 20 carbon atoms, especially 6 to 14 carbon atoms, as a ring component. Aryl is preferably phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrycenyl, pyrenyl, coronenyl, perylenyl, and more preferably phenyl or naphthyl.

Depending on the number and size of the ring system, the substituted aryl may have one or more (eg, 1, 2, 3, 4, 5, 6 or more) substituents. These are each independently alkyl and alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkyl Carbonyloxy, carbamoyl, SO ₃ H, sulfonate, sulfamino, sulfamide, amidino, NE ⁵ E ^{6 where} E ⁵ and E ⁶ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl Is preferably selected from the group consisting of The alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, and hetaryl substituents on the aryl may each be unsubstituted or substituted.

  For these groups, see the substituents described above. The substituent on aryl is preferably selected from alkyl and alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano, nitro. Substituted aryl is more preferably substituted phenyl with generally 1, 2, 3, 4 or 5 substituents, preferably 1, 2 or 3 substituents. is there.

  The substituted aryl is preferably aryl substituted with at least one alkyl group (“alkaryl”, hereinafter also referred to as alkylaryl). Depending on the size of the aromatic ring system, the alkaryl group may contain one or more (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10). The above may have an alkyl substituent. These alkyl substituents may be unsubstituted or substituted. In this regard, reference is made to the above description regarding unsubstituted and substituted alkyl. In certain preferred embodiments, these alkaryl groups are fully unsubstituted alkyl substituents. The alkaryl preferably has 1, 2, 3, 4 or 5 alkyl substituents, preferably 1, 2 or 3, more preferably 1 or 2 alkyl substituents. A phenyl having a group.

  Aryl having one or more groups is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6 trimethyl Phenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2 , 4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5 -, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2 , 6-Diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2 , 6-Di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- And 2,6-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- And 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethoxy Phenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3 -And 4-isopropoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl, 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4 -Chlorophenyl, (2-chloro-6-methyl) phenyl, (2-chloro-6-ethyl) phenyl, (4-chloro-6-methyl) phenyl, (4-chloro-6-ethyl) phenyl That.

  The above definition for aryl also applies to aryl groups in aryloxy and arylthio (= arylsulfanyl), monoarylamino, diarylamino.

In the present invention, “heterocycloalkyl” generally means a non-aromatic, unsaturated or fully saturated alicyclic group having 5 to 8 ring atoms, preferably 5 or 6 ring atoms. including. In these heterocycloalkyl groups, one, two, three, four, five or more ring carbon atoms are substituted with a heteroatom or a heteroatom-containing group as compared to the corresponding cycloalkyl group. Yes. This heteroatom or heteroatom-containing group is preferably selected from —O—, S—, NR ^e —, C (═O), S (═O) and / or —S (═O) ₂ —. R ^e is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Heterocycloalkyl is unsubstituted or has one or more (eg, 1, 2, 3, 4, 5, 6, or 7) identical or different groups if necessary. These are independently alkyl and alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxy Rate, alkylcarbonyloxy, carbamoyl, SO ₃ H, sulfonate, sulfamino, sulfamide, amidino, NE ⁵ E ⁶ (wherein E ⁵ and E ⁶ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, Preferably aryl or hetaryl). Examples of heterocycloalkyl groups are in particular pyrrolidinyl and piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl , Tetrahydrothiophenyl, dihydrothien-2-yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropyranyl, 2-oxazolinyl, 3-oxazolinyl, 4-oxazolinyl, dioxanyl.

The substituted heterocycloalkyl group may have one or more (eg, 1, 2, 3, 4, 5, 6 or more) substituents depending on the size of the ring. These are each independently alkyl and alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkyl Carbonyloxy, carbamoyl, SO ₃ H, sulfonate, sulfamino, sulfamide, amidino, NE ⁷ E ^{8 where} E ⁷ and E ⁸ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl Is preferably selected from the group consisting of When substituted, these heterocycloalkyl groups preferably have one or more (eg, one, two, three, four, or five) C ₁ -C ₆ -alkyl groups.

  The above definition for heterocycloalkyl also applies to heterocycloalkyl groups in heterocycloalkoxy and heterocycloalkylthio (= heterocycloalkylsulfanyl), monoheterocycloalkylamino, diheterocycloalkylamino.

  In the present invention, “hetaryl” (heteroaryl) includes heteroaromatic monocyclic or polycyclic groups. In addition to the ring carbon atoms, these contain 1, 2, 3, 4, 5 or more heteroatoms as ring components. This heteroatom is preferably selected from oxygen, nitrogen, selenium, and sulfur. These hetaryl groups preferably have 5 to 18 ring atoms, for example, 5, 6, 8, 9, 10, 11, 12, 13 or 14 ring atoms. .

  The monocyclic hetaryl group is preferably a 5- or 6-membered hetaryl group, and specifically includes 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2- Thienyl (thiophen-2-yl), 3-thienyl (thiophen-3-yl), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrole- 1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4- Oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazo 2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H- [1,2, 4] -Triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl , Pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1, 2,4-Triazin-3-yl.

  Polycyclic hetaryl groups have 2, 3, 4, 5 or more fused rings. These fused rings may be aromatic rings or saturated or partially unsaturated rings. Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzoxdiazolyl, benzo Thiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thienothiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofura Nyl, dibenzothiophenyl, naphtho [2,3-b] thiophenyl, naphtha [2,3-b] furyl, dihydroindolyl, dihydroindolidinyl, dihydroisoindolyl, dihydroquinolinyl, dihydroisoquinolinyl In The

The substituted hetaryl group may have one or more (eg, 1, 2, 3, 4, 5, 6 or more) substituents depending on the number and size of the ring system. These are independently alkyl and alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, Alkylcarbonyloxy, carbamoyl, SO ₃ H, sulfonate, sulfamino, sulfamide, amidino, NE ⁹ E ^{10 wherein} E ⁹ and E ¹⁰ are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or It is preferably selected from hetaryl. The halogen substituent is preferably fluorine, chlorine or bromine. Substituents, C ₁ -C ₆ - alkyl and C ₁ -C ₆ - alkoxy, hydroxyl, carboxyl, halogen, be selected from cyano preferred.

  The above definition for hetaryl also applies to hetaryl groups in hetaryloxy and hetarylthio, monohetarylamino, dihetarylamino.

  Preferably, in the compound of the general formula (I), the metal atom-containing group M is a metal selected from groups 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 of the periodic table. It is preferable to include. Preferred metals are Ti and Zr, Cr, Mo, W, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, In, and B.

  Particularly preferred are compounds of general formula (I) wherein M is a group containing Pd (II), Pt (II) or Au (I).

Suitable groups M is, in principle, a formula L _y Me-group. Me is a metal, L is a ligand, and y is an integer that depends on the valence and type of the metal and the number of coordination positions occupied by each ligand L. Suitable ligands L are independently F and Cl, Br, I, CO, isonitrile, nitrile, amine, carboxylate, acetylacetonate, hydride, olefin, cycloolefin, diene, alkyne, C ₅ H ₅ ^- , C ₇ H ₇ ⁺ , N-containing heterocycle, aromatic, heteroaromatic, ether, PF ₃ , phosphole, phosphabenzene, phosphine (e.g. P (C ₆ H ₅ ) ₃ , P (CH ₃ ) C ₆ H ₅ ) ₂ , P (CH ₃ ) ₂ (C ₆ H ₅ ), P (CH ₃ ) ₃ , dppe (1,2-ethanediylbis [(diphenyl) phosphine]), P (C ₆ H ₁₁ ) ₃ Etc.), phosphinite, phosphonite, phosphite, alkyl sulfonate, aryl sulfonate and the like.

In particular, in the compound of general formula (I), M is PdCl ₂ (CNR ¹ ), PtCl ₂ (CNR ¹ ), PdCl (CNR ¹ ) ₂ , Au (CNR ¹ ), AuCl (where R ¹ is Selected from hydrogen and alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl.

R ¹ is preferably selected from the group of the formulas IV.1 to IV.5, in particular the groups of the formulas IV.1 and IV.2 are preferred.

In the formula
# Indicates the bond position to the nitrogen atom,
p is 0 or 1,
x is 2 or 3 (when x is 2, the carbon atom having the R ⁱ group further has one hydrogen atom);
X _{1 in} formulas IV.2 and IV.3 and IV.4 is 0, ₁ , 2, 3, 4, or 5;
X _{2 in} formulas IV.2, IV.3 and IV.4 is 0 or 1;
(Wherein the sum of x ₁ and x ₂ in formulas IV.2, IV.3 and IV.4 is 0, ₁ , ₂ , 3, 4 or 5),
X _{1 in} formula IV.5 is 0, 1 or 2;
X _{2 in} formula IV.5 is 0 or 1;
(Wherein the sum of x ₁ and x ₂ in formula IV.5 is 0, 1 or 2),
When present, A is a C ₁ -C ₁₀ -alkylene group interrupted by one or more non-adjacent groups selected from —O— and S—
Each R ⁱ group is independently C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -alkyloxy or C ₁ -C ₃₀ -alkylthio (note that at least one alkyl chain in alkyl, alkyloxy or alkylthio has one or more And may be interrupted by non-adjacent oxygen atoms.

More preferably, in formulas IV.2, IV.3 and IV.4, x ₁ is 0, ₁ , 2 or 3 and x ₂ is 0 or 1. (However, the sum of x ₁ and x ₂ is 0, 1, 2 or 3.)
More preferably, R ¹ is selected from phenyl having a group selected from C ₁ -C ₆ -alkyl and phenyl, 1, 2 or 3 independently from C ₁ -C ₆ -alkyl and chlorine. In particular, R ¹ is isopropyl and tert-butyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2, 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 3,5-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 2,4-dipropylphenyl, 2,5-dipropylphenyl, 3,5 -Dipropylphenyl, 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,5-diisopropyl Phenyl, 3,5-diisopro Ruphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-butylphenyl, 3-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,5-dibutylphenyl, 3, 5-dibutylphenyl, 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-isobutylphenyl, 3-isobutylphenyl, 4-isobutylphenyl, 2,4-diisobutylphenyl, 2,5-diisobutylphenyl, 3,5-diisobutylphenyl, 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-sec-butylphenyl, 3-sec-butylphenyl, 4-sec-butylphenyl, 2,4-di -sec-butylphenyl, 2,5-di-sec-butylphenyl, 3,5-di-sec-butylphenyl, 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-butyl Phenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2,4- Di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4,6-tri-tert- Butylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, (2-chloro-6-methyl) phenyl, (2-chloro-6-ethyl) phenyl, (2-chloro-6-propyl) phenyl, (2 -Chloro-6-isopropyl) phenyl, (2-chloro-6-butyl) phenyl, (2-chloro-6-isobutyl) phenyl, (2-chloro-6-sec-butyl) phenyl, (2-chloro-6 Selected from -tert-butyl) phenyl.

In particular, R ¹ is selected from tert-butyl and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, (2-chloro-6-methyl) phenyl.

Preferably R ² is selected from hydrogen and alkyl, cycloalkyl, in particular C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, C ₅ -C ₁₅ -cycloalkyl.

More preferably, R ² is from methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 1-phenylethyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, 1-adamantyl. To be elected.

In a first preferred embodiment, R ³ and R ⁴ are independently selected from hydrogen and unsubstituted or substituted aryl. When at least one of the remaining R ³ and R ⁴ is aryl, this remaining group is preferably phenyl. In particular, R ³ and R ⁴ are both hydrogen.

In a second preferred embodiment, R ³ and R ⁴ are C═O together with the carbon atom to which they are attached.

In a third preferred embodiment, R ³ is an OR ^3a group, wherein R ^3a is bonded to oxygen via a carbon atom, silicon atom, sulfur atom, phosphorus, boron or titanium atom. Group). In this embodiment, in the compound of general formula (I), when n is 0, the remaining groups R ⁴ and R ⁷ have the same bond as the double bond between carbon atoms having R ⁴ and R ^7. Represent. In this embodiment, in the compound of general formula (I), when n is 1, the remaining groups R ⁴ and R ⁵ have the same bond as the double bond between carbon atoms with R ⁴ and R ^5. Represent.

Preferably R ³ is selected from the group of formula VA, VB, VC, VD, VE, VF, VG, VH, VI, VK or VL, more preferably from the group of formula VA, VB or VC. It is.

In the formula
# Represents the bonding position to the oxygen atom,
T is selected from -O- and NR ^{Vf where} R ^Vf is hydrogen, alkyl, cycloalkyl or aryl;
R ^Va and R ^Vb are selected from unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl,
R ^Vc and R ^Vd and R ^Ve are each independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl,
R ^Vg is selected from unsubstituted or substituted heterocycloalkyl,
R ^Vh is selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl,
R ^Vi and R ^Vk are each independently an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, an alkoxy, an unsubstituted or substituted aryloxy, an unsubstituted or substituted Selected from cycloalkyloxy,
R ^Vm and R ^Vn are each independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl. And
R ^Vo and R ^Vp are each independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl. And
R ^Vq , R ^Vr and R ^Vs are each independently an unsubstituted or substituted alkyl, an unsubstituted or substituted alkenyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, an unsubstituted or substituted Chosen from hetaryl,
R ^Vt , R ^Vu and R ^Vv are each independently an unsubstituted or substituted alkyl, an unsubstituted or substituted alkenyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, an unsubstituted or substituted Chosen from hetaryl,
R ^Vw , R ^Vx and R ^Vy are each independently selected from unsubstituted or substituted alkyloxy, unsubstituted or substituted alkenyloxy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aryloxy. Is;
D ⁺ is a cation equivalent.

This cation equivalent D ⁺ merely acts as a counter ion and can be freely selected from monovalent cations and from some of the multivalent cations corresponding to a single positive charge. Suitable cations are, for example, alkali metal ions D ⁺ such as Na + and K +, alkaline earth metal cations such as Ca2 ⁺ , and ammonium ions.

Preferably, R ^Va is unsubstituted phenyl or C ₁ -C _4, - alkyl and C ₁ -C ₄ - alkoxy, one selected from independently from nitro, substituted with two or three groups Phenyl.

Preferably, R ^Vb is (C ₁ -C ₄ -alkyl) phenyl, and the phenyl group of this (C ₁ -C ₄ -alkyl) phenyl is C ₁ -C ₄ -alkyl, even if unsubstituted. And may be substituted with 1, 2 or 3 groups independently selected from C ₁ -C ₄ -alkoxy and nitro.

T is preferably O. In the group of formula VB, T is preferably O, R ^Vb is benzyl, phenyl group benzyl can be unsubstituted or substituted, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - It may be substituted with 1, 2 or 3 groups independently selected from alkoxy and nitro.

R ^Vc and R ^Vd and R ^Ve are each independently C ₁ -C ₆ -alkyl, C ₅ -C ₁₀ -cycloalkyl, and may be unsubstituted, C ₁ -C ₄ -alkyl and It is preferably selected from C ₁ -C ₄ -alkoxy and phenyl optionally substituted by 1, 2 or 3 groups independently selected from nitro. Examples of the group VC are trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethylisopropylsilyl, diethylisopropylsilyl, dimethylhexylsilyl, 2-norbornyldimethylsilyl, tert-butyldimethylsilyl, di-tert-butylmethylsilyl, tert -Butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl, diphenylmethylsilyl.

  It is preferred that the group of formula VD is 2,2,5,5-tetramethylpyrrolidin-3-one-1-sulfinate.

Preferably, R ^Vh is C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkyl substituted with phenyl (even though phenyl is unsubstituted, C ₁ -C ₄ -Alkyl and C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, substituted with 1, 2 or 3 groups independently selected from nitro may be), C ₂ -C ₆ - alkenyl, benzyl, phenyl (phenyl may be unsubstituted or substituted, C ₁ -C ₄ - alkyl and C ₁ -C ₄ - haloalkyl, C ₁ -C ₄ - halo Optionally substituted by 1, 2 or 3 groups independently selected from alkoxy, C ₁ -C ₄ -alkoxy, nitro). Examples of groups of the formula VE are methanesulfonic acid and trifluoromethanesulfonate, 2-[(4-nitrophenyl) ethyl] sulfonate, allylsulfonate, benzylsulfonate, tosylate, 2-trifluoromethylbenzenesulfonate.

R ^Vi and R ^Vk are each independently C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy, and may be unsubstituted, C ₁ -C ₄ -alkyl and C ₁ -C ₄ - haloalkyl, C ₁ -C ₄ - haloalkoxy, C ₁ -C ₄ - 1 pieces selected from independently alkoxy, be selected from two or three phenyl optionally substituted with a group preferred

It is preferred that R ⁷ and R ^{8 and} , if present, R ⁵ and R ⁶ are independently selected from hydrogen and unsubstituted or substituted aryl. When the radicals R ⁷ and R ⁸ and, if present, at least one of R ⁵ and R ⁶ are aryl, this radical is preferably phenyl. In a first preferred embodiment, R ⁷ and R ^{8 and} , if present, R ⁵ and R ⁶ are all hydrogen. In a second preferred embodiment, one of the groups selected from R ⁷ and R ^{8 and} , if present, R ⁵ and R ⁶ is phenyl, and the other groups are all hydrogen.

In a particular embodiment, the two groups R ² and R ⁸ together with the N atom to which R ² is attached and the carbon atom to which R ⁸ is attached have a 3-, 4-, 5-, 6-, 7- , 8-, 9-, 10-, 11- or 12-membered unsubstituted or substituted nitrogen heterocycle, optionally as a ring component, independently O and N, NR ^a (R ^a is hydrogen, alkyl , Cycloalkyl or aryl), may have one, two or three other heteroatoms or heteroatom-containing groups selected from S. Suitable substituents on the nitrogen heterocyclic ring of 3-membered to 12-membered ring, preferably a halogen and cyano, nitro, hydroxy, mercapto, amino, carboxyl, C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkoxy C ₂ -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkylthio, and / or a 3- to 12-membered heterocyclic ring Together with the above atoms, the two substituents bonded to the adjacent atoms are fused benzene ring, fused naphthalene ring, condensed saturated or partially unsaturated 5-, 6-, or 7-membered carbocyclic ring or condensed 5-, 6-, or a heterocyclic ring 7 membered ring, oxygen and sulfur as a ring component, (wherein, R ^a is as defined above) NR ^a 1, 2, 3 or 4 selected from The fused ring is unsubstituted or halogen and cyano, nitro, hydroxy, mercapto Amino, carboxyl, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, C ₁ -C ₆ -haloalkoxy, C ₁ A heterocyclic ring optionally having 1, 2, 3, or 4 groups of any combination selected from -C ₆ -alkylthio may be formed.

  Compounds of general formula (ID) are preferred.

(Wherein n and M, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are preferably those having the above meanings, and have the meanings described as being particularly preferred). In particular, n is 0, M is selected from PdCl ₂ (CNR ¹ ) and PdCl (CNR ¹ ) ₂ , PtCl ₂ (CNR ¹ ), Au (CNR ¹ ), AuCl, R ¹ is tert-butyl And 2,6-dimethylphenyl, 2,4,6 trimethylphenyl, 2,6 diisopropylphenyl, (2-chloro-6-methyl) phenyl, and R ³ and R ⁴ are both hydrogen.

  In the first variant above, the process according to the invention comprises a compound of formula (I-A.1) or (IA-.2):

(Where
M and R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ have the meanings described above as being particularly preferable,
R ³ and R ⁴ are independently hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) ) Amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino).

  In a preferred embodiment of the first variant, the process of the invention comprises a compound of general formula (I-A.2.1):

(Wherein M and R ¹ , R ² , R ³ , R ⁷ have the above-mentioned meanings, the meanings described as being particularly preferable). (In formula IA.2.1, the groups R ⁴ and R ⁸ are hydrogen and are not shown.)

Compounds of general formula (I-A.2.2) shown in Tables 1 to 5 below are preferred embodiments of the present invention. The meanings of R ¹ , R ^2, and R ³ in Table A below are the same, even if they are independent from each other or particularly in combination.

Table 1
A compound of the formula (I-A.2.2), in which the group M is PdCl ₂ (CNR ¹ ) and any combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table A . Group R ¹ in bonded to a ring nitrogen atom are groups R ¹ and groups PdCl ₂ (CNR ¹⁾ are both have the same meaning. Compared to general formula (I), in formula (I-A.2.2) n is 0 and the radicals R ⁴ , R ⁷ and R ⁸ are hydrogen and are not shown.

Table 2
In the compound of formula (I-A.2.2), the group M is PtCl ₂ (CNR ¹ ), and the combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table A in any case. thing. Group R ¹ in bonded to a ring nitrogen atom group R ¹ and group PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 3
A compound of formula (I-A.2.2) in which the group M is PdCl (CNR ¹ ) ₂ and the combination of R ¹ , R ² and R ³ of a compound is Equivalent. Group R ¹ ring nitrogen atom bonded are based on R ¹ and group PdCl (CNR ¹⁾ ₂ are both have the same meaning.

Table 4
A compound of formula (I-A.2.2), in which the group M is AuCl, and the combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table A in each case.

Table 5
A compound of formula (I-A.2.2), wherein the group M is Au (CNR ¹ ), and the combination of R ¹ , R ² and R ³ of a certain compound corresponds to one row of Table A in any case What to do. Bonded to a ring nitrogen atom by which group R ¹ and the group AuCl (CNR ¹⁾ groups R ¹ in the both have the same meaning.

  In a preferred embodiment of the second variant above, the process according to the invention comprises a compound of general formula (I-B.1) or (I-B.2):

(Where
M and R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the above-mentioned meanings, and the meanings described as being particularly preferable).
In a particularly preferred embodiment of the second variant, the process according to the invention is a compound of the general formula (I-B.2.1):

(Wherein M, R ¹ and R ² have the above meanings, particularly preferred meanings) are used in the production.

Compounds of general formula (IB.2.1) shown in Tables 6-10 below are preferred embodiments of the present invention. The meanings of R ¹ and R ² shown in Table B below indicate preferred embodiments of the present invention even if they are independent of each other or in particular combinations.

Table 6
A compound of the formula (I-B.2.1) in which the group M is PdCl ₂ (CNR ¹ ) and the combination of R ¹ and R ² of a compound corresponds to one row of Table B. Group R ¹ in bonded to a ring nitrogen atom are groups R ¹ and groups PdCl ₂ (CNR ¹⁾ are both have the same meaning. Compared to general formula (I), in formula (I-B.2.1), n is 0 and the radicals R ⁷ and R ⁸ are hydrogen and are not shown.

Table 7
A compound of the formula (I-B.2.1), in which the group M is PtCl ₂ (CNR ¹ ) and any combination of R ¹ and R ² of a compound corresponds to one row of Table B. Group R ¹ in bonded to a ring nitrogen atom are groups R ¹ and groups PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 8
A compound of formula (I-B.2.1), in which the group M is PdCl (CNR ¹ ) ₂ and any combination of R ¹ , R ² and R ^{3 of} a compound corresponds to one row of Table B thing. Groups R ¹ ring nitrogen atom bonded are based on R ¹ and group PdCl (CNR ¹⁾ ₂ are both have the same meaning.

Table 9
A compound of the formula (I-B.2.1), in which the group M is AuCl and any combination of R ¹ and R ² of a compound corresponds to one row of Table B.

Table 10
A compound of formula (I-B.2.1), in which the group M is Au (CNR ¹ ), and any combination of R ¹ and R ² of a compound corresponds to one row of Table B. Bonded to a ring nitrogen atom by which group R ¹ and the group AuCl (CNR ¹⁾ groups R ¹ in the both have the same meaning.

  In a preferred embodiment of the third variant, the process according to the invention is a compound of the general formula (I-C.1) or (I-C.2):

(Wherein M and R ¹ , R ² , R ^3a , R ⁶ , R ⁷ , R ⁸ have the above-mentioned meanings, and particularly preferred meanings).

  In a particularly preferred embodiment of the third variant, the process according to the invention is a compound of the general formula (I-C.2.1):

(Wherein M, R ¹ , R ² , and R ^3a have the above-mentioned meanings, and the meanings described as being particularly preferable).

Compounds of general formula (I-C.2.1) shown in Tables 11 to 15 below are preferred embodiments of the present invention. The meanings of R ¹ , R ² and R ³ shown in Table C below indicate preferred embodiments of the present invention independently of one another and in particular in combination as well.

Table 10
A compound of the formula (I-C.2.1), in which the group M is PdCl ₂ (CNR ¹ ) and any combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table C What to do. Group R ¹ in bonded to a ring nitrogen atom are groups R ¹ and groups PdCl ₂ (CNR ¹⁾ are both have the same meaning. Compared to general formula (I), in formula (I-C.2.1), n is 0 and the group R ⁸ is hydrogen and is not shown.

Table 11
A compound of formula (I-C.2.1), in which the group M is PtCl ₂ (CNR ¹ ) and any combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table C What to do. Group R ¹ in the group R ¹ and group PdCl ₂ attached to a ring nitrogen atom (CNR ¹⁾ are both have the same meaning.

Table 12
A compound of formula (I-C.2.1), wherein the group M is PdCl (CNR ¹ ) ₂ and the combination of R ¹ , R ² and R ³ of a compound is Equivalent. Group R ¹ ring nitrogen atom bonded are based on R ¹ and group PdCl (CNR ¹⁾ ₂ are both have the same meaning.

Table 14
A compound of formula (I-C.2.1), in which the group M is AuCl, and any combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table C.

Table 15
A compound of formula (I-C.2.1), in which the group M is Au (CNR ¹ ), and any combination of R ¹ , R ² and R ³ of a compound corresponds to one row of Table C thing. Group R ¹ in the ring nitrogen atom bonded to that group R ¹ and the group Au (CNR ¹⁾ are both have the same meaning.

  In a preferred embodiment of the second aspect, the method of the invention comprises a compound of general formula IE:

(Wherein M and R ¹ , R ² , R ³ and R ⁸ have the above-mentioned meanings).

In this embodiment, R ¹ and R ² preferably have different meanings. R ¹ is preferably selected from the group of formulas IV.1 to IV.5, with formulas IV.1 and IV.2 being particularly preferred. More preferably, R ¹ is selected from C ₁ -C ₆ -alkyl and phenyl, independently phenyl having 1, 2 or 3 groups selected from C ₁ -C ₆ -alkyl and chlorine. Particularly preferably R ¹ is selected from tert-butyl and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, (2-chloro-6-methyl) phenyl.

Preferably, R ² is selected from alkyl and cycloalkyl, in particular C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, C ₅ -C ₁₅ -cycloalkyl. In particular, R ² is selected from methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, cyclododecyl, 1-adamantyl.

Preferably R ³ is selected from hydrogen and alkyl, cycloalkyl, aryl, more preferably from hydrogen and C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl.

Preferably R ⁸ is selected from hydrogen and alkyl, cycloalkyl, aryl, more preferably from hydrogen and C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl.

M is preferably PdCl ₂ (CNR ¹ ) and PtCl ₂ (CNR ¹ ), PdCl (CNR ¹ ) ₂ , Au (CNR ¹ ), AuCl (where R ¹ is hydrogen and alkyl, cycloalkyl, heterocycloalkyl , Aryl, and hetaryl).

  In a particularly preferred embodiment of the second aspect, the process of the invention is a compound of formula I-E.1:

(Wherein M, R ¹ and R ² have the above-mentioned meanings, the meanings described as being particularly preferred).

Compounds of general formula (I-E.1) shown in Tables 16-20 below are preferred embodiments of the present invention. The meanings of R ¹ and R ² shown in Table D below indicate the preferred embodiments of the invention independently of one another and in particular in combination as well.

Table 16
A compound of the formula (I-E.1), in which the group M is PdCl ₂ (CNR ¹ ) and the combination of R ¹ and R ² of a compound corresponds in each case to one row of Table D . Group R ¹ in bonded to a ring nitrogen atom group R ¹ and group PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 17
A compound of the formula (I-E.1), in which the group M is PtCl ₂ (CNR ¹ ) and the combination of R ¹ and R ² of a compound corresponds in each case to one row of Table D . Group R ¹ in the group R ¹ and group PdCl ₂ attached to a ring nitrogen atom (CNR ¹⁾ are both have the same meaning.

Table 18
A compound of the formula (I-E.1), in which the group M is PdCl (CNR ¹ ) ₂ and the combination of R ¹ and R ² of a compound corresponds in each case to one row of Table D . Group R ¹ ring nitrogen atom bonded are based on R ¹ and group PdCl (CNR ¹⁾ ₂ are both have the same meaning.

Table 19
A compound of the formula (I-E.1), in which the group M is AuCl and the combination of R ¹ and R ² of a compound corresponds to one row of Table D in each case.

Table 20
A compound of the formula (I-E.1), in which the group M is Au (CNR ¹ ) and the combination of R ¹ and R ² of a compound corresponds to one row of Table D in each case. Group R ¹ in the ring nitrogen atom bonded to that group R ¹ and the group Au (CNR ¹⁾ are both have the same meaning.

  In a preferred embodiment of the third aspect, the process of the invention comprises a compound of general formula IF:

(Wherein M and EWG, R ¹ , R ² , R ⁴ , R ⁷ and R ⁸ have the above-mentioned meanings).
In this embodiment, R ¹ and R ² preferably have different meanings. Phenyl having one selected from haloalkyl, two or three groups - In this exemplary aspect, R ¹ is preferably phenyl and naphthyl, independently C ₁ -C ₈ and - alkyl and C ₁ -C ₈ also independently C ₁ -C ₈ and - alkyl and C ₁ -C ₈ - 1 pieces selected from haloalkyl, selected from naphthyl having two or three groups, particularly C ₁ -C ₆ - alkyl or C Selected from ₁ -C ₆ -fluoroalkyl. In particular, R ¹ is 2,6-dimethylphenyl and 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, 2,6-di- (trifluoromethyl) phenyl, 1 -Selected from naphthyl and 2-naphthyl.

Preferably, R ² is selected from alkyl and cycloalkyl, in particular C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, C ₅ -C ₁₅ -cycloalkyl. More preferably, R ² is selected from methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 1-phenylethyl, cyclopentyl, cyclohexyl, cyclododecyl, 1-adamantyl .

Preferably R ⁴ is selected from hydrogen and alkyl, cycloalkyl, aryl, more preferably from hydrogen and C ₁ -C ₁₀ -alkyl.

Preferably, R ⁷ and R ⁸ are independently selected from hydrogen and alkyl, cycloalkyl, and aryl, more preferably selected from hydrogen and C ₁ -C ₁₀ -alkyl.

EWG is preferably C (O) R ¹⁴ or C (O) OR ¹⁴ , in particular C (O) OR ¹⁴ . In this embodiment, R ¹⁴ is preferably C ₁ -C ₆ -alkyl, in particular C ₁ -C ₄ -alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- Butyl, isobutyl or tert-butyl.

M is preferably PdCl ₂ (CNR ¹ ) and PtCl ₂ (CNR ¹ ), PdCl (CNR ¹ ) ₂ , Au (CNR ¹ ), AuCl (wherein R ¹ is hydrogen and alkyl, cycloalkyl, hetero Selected from cycloalkyl, aryl, and hetaryl.

  Compounds of formula IF-1 are preferred:

(Where EWG and M, R ¹ and R ² have the meanings given above, preferably as preferred).

Compounds of general formula (I-F.1) shown in Tables 21-30 are a preferred embodiment of the present invention. The meanings of R ¹ and R ² shown in Table E indicate the preferred embodiments of the invention independently of one another and in particular in combination as well.

Table 21
A compound of formula (I-F.1), wherein the group M is PdCl ₂ (CNR ¹ ), EWG is methoxycarbonyl, and the combination of R ¹ and R ² of a compound is E equivalent to one line. Group R ¹ in bonded to a ring nitrogen atom group R ¹ and group PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 22
A compound of formula (I-F.1), wherein the group M is PtCl ₂ (CNR ¹ ), EWG is methoxycarbonyl, and the combination of R ¹ and R ² of a compound is E equivalent to one line. Group R ¹ in bonded to a ring nitrogen atom group R ¹ and group PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 23
A compound of formula (I-F.1), wherein the group M is PdCl (CNR ¹ ) ₂ , EWG is methoxycarbonyl, and the combination of R ¹ and R ² of a compound is E equivalent to one line. Group R ¹ ring nitrogen atom bonded are based on R ¹ and group PdCl (CNR ¹⁾ ₂ are both have the same meaning.

Table 24
A compound of formula (I-F.1), wherein the group M is AuCl, EWG is methoxycarbonyl, and the combination of R ¹ and R ² of a compound corresponds to one row in Table E in each case What to do.

Table 25
A compound of formula (I-F.1), wherein the group M is Au (CNR ¹ ), the EWG is methoxycarbonyl, and the combination of R ¹ and R ² of a compound in each case is shown in Table E Equivalent to one line. Group R ¹ in the ring nitrogen atom bonded to that group R ¹ and the group Au (CNR ¹⁾ are both have the same meaning.

Table 26
A compound of formula (I-F.1), wherein the group M is PdCl ₂ (CNR ¹ ), EWG is ethoxycarbonyl, and the combination of R ¹ and R ² of a compound is Equivalent to one row in Table E. Group R ¹ in bonded to a ring nitrogen atom group R ¹ and group PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 27
A compound of formula (I-F.1), wherein the group M is PtCl ₂ (CNR ¹ ), EWG is ethoxycarbonyl, and the combination of R ¹ and R ² of a compound is E equivalent to one line. Group R ¹ in bonded to a ring nitrogen atom group R ¹ and group PdCl ₂ (CNR ¹⁾ are both have the same meaning.

Table 28
A compound of formula (I-F.1), wherein the group M is PdCl (CNR ¹ ) ₂ , EWG is ethoxycarbonyl, and the combination of R ¹ and R ² of a compound is E equivalent to one line. Group R ¹ ring nitrogen atom bonded are based on R ¹ and group PdCl (CNR ¹⁾ ₂ are both have the same meaning.

Table 29
A compound of formula (I-F.1), wherein the group M is AuCl, EWG is ethoxycarbonyl, and the combination of R ¹ and R ² of a compound corresponds to one row of Table E in each case What to do.

Table 30
A compound of formula (I-F.1), wherein the group M is Au (CNR ¹ ), EWG is ethoxycarbonyl, and the combination of R ¹ and R ² of a compound in each case Equivalent to one line. Group R ¹ in the ring nitrogen atom bonded to that group R ¹ and the group Au (CNR ¹⁾ are both have the same meaning.

Step a1)
In step a1) of the process according to the invention, an isonitrile complex R ¹ —N≡CM of the general formula (II) (wherein R ¹ and M have one of the above meanings) is used.

Synthesis of Isonitrile Ligands Synthesis of isonitriles suitable to give isonitrile complexes of general formula (II) can be carried out in a conventional manner from commercially available precursors or precursors obtained by known methods, which are described below. Briefly described. Suitable methods for the synthesis of isonitriles are, for example, dehydration from N-substituted formamides, reaction of primary amines with chloroform under basic conditions (haloform-isocyanide conversion), and reduction of isocyanates. A preferred method for obtaining isonitriles of the general formula R ¹ —N≡C is to react the amine R ¹ —NH ₂ with formate at the elevated temperature shown in Scheme 1 to give the formula R ¹ —NH—CH (═O) And then dehydrating, for example, using POCl ₃ and a tertiary amine, phosgene and a tertiary amine, and the like.

Scheme 1:

In scheme 1, R ¹ has the meaning mentioned above, particularly preferred, and Et means ethyl.

Synthesis of isonitrile complexes of general formula (II) In the process of the present invention, the desired metal carbene complex is formed from an isonitrile ligand (isocyanide ligand) coordinated to the metal. The isonitrile complex R ¹ -N≡CM of the general formula (II) used is readily available, for example, by the above-mentioned isonitrile compounds R ¹ -N≡C and ligand exchange reactions known to those skilled in the art. From a complex of metal M, it can be obtained as shown in Scheme 2. Preferred educt complexes are, for example, [Pd (CH ₃ CN) ₂ Cl ₃ ], [Pt (CH ₃ CN) ₂ Cl ₂ ], [AuCl (tetrahydrothiophene)].

  Scheme 2 (Synthesis of Pd (II)-, Au (I)-and Pt (II) -isonitrile complexes):

In scheme 2, R ¹ has the meaning described above as being particularly preferred.

Synthesis of NHC Complex To obtain the desired NHC complex, an isonitrile complex of general formula (II) is reacted with a compound of general formula (III) or (IIIa).

(Where
n and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ have one of the above meanings,
X ^- is an anion equivalent,
Y is a leaving group, or when R ³ and R ⁴ together with the carbon atom to which it is attached is C═O, Y is a group OY ^{a where} Y ^a is an unsubstituted or substituted alkyl , Unsubstituted or substituted aryl, unsubstituted or substituted alkylcarbonyl, or unsubstituted or substituted arylcarbonyl).

This anion equivalent X ⁻ serves merely as a counter ion and can be freely selected from a monovalent anion and a part of a polyvalent anion corresponding to a single charge. Suitable anions are, for example, halogen ions X ⁻ such as chloride ions and bromine ions, and sulfuric acid and sulfonic acid anions such as SO ₄ ²⁻ , tosylate, trifluoromethanesulfonate, and methanesulfonic acid. Preferably, X ⁻ is a chlorine ion or a bromine ion.

  Preferably, Y is selected from halogen ions and tosylate, carboxylate, carbonate, ester, sulfonate, phosphate. Examples of Y are chlorine, bromine, iodine, methanesulfonic acid, trifluoromethanesulfonate, and toluenesulfonic acid, with chlorine and bromine being preferred.

Preferably, Y ^a is selected from C ₁ -C ₄ -alkyl and pentafluorophenylcarbonyl.

  In a first preferred embodiment, the compound of formula (III) is an ω-haloalkylammonium salt, preferably 2- (haloethyl) ammonium halide or 3- (halopropyl) ammonium halide. Similarly, in another first preferred embodiment, the compound of formula (III.a) is an ω-haloalkylamine, preferably 2- (haloethyl) amine or 3- (halopropyl) amine.

  In particular, the compound of formula (III) is 2- (chloroethyl) ammonium chloride of formula (III.1) and the compound of formula (III.a) is 2- (chloroethyl) of formula (III.1.a) It is an amine.

(Where
R ² is selected from alkyl and cycloalkyl, in particular C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, C ₅ -C ₁₅ -cycloalkyl.
R ³ and R ⁴ , R ⁷ and R ⁸ are selected from hydrogen, C ₁ -C ₆ -alkyl and C ₆ -C ₁₀ -aryl. )

In compounds (III.1) and (III.1.a), R ² is methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclododecyl, It is preferably selected from 1-adamantyl.

In the compounds (III.1) and (III.1.a), R ³ and R ⁴ , R ⁷ and R ⁸ are preferably selected from hydrogen and phenyl. In a special embodiment, R ³ and R ⁴ , R ⁷ and R ⁸ are all hydrogen. In another particular embodiment, one of the groups R ³ and R ⁴ , R ⁷ , R ⁸ is phenyl and the other is hydrogen.

  The preparation of ω-haloalkylammonium salt (III) and its free base, ie ω-haloalkylamine compound (III.a), can be carried out by conventional methods, and the preparation of ω-chloroalkylammonium salt is shown in Scheme 3. Thus, the synthesis of 2- (chloroethyl) ammonium chloride can be performed from commercially available aminoalcohols by literature methods (eg, A. Habtemariam et al., J. Chem. Soc. Dalton Trans. 2001, 8, 1306- (See 1318). The free amine of formula (III.1.a) is formed from the salt of formula (III.1) by addition of a base. A suitable base is, for example, a tertiary amine such as triethylamine.

Scheme 3 (Synthesis of 2- (chloroethyl) ammonium chloride and 2- (chloroethyl) amine compound)

In Scheme 3, R ² and R ³ , R ⁴ , R ⁷ , R ⁸ have the above-mentioned meanings, and the meanings described as being particularly preferable.

  Synthesis of 2- (adamantan-1-ylamino) ethanol as a starting material for the synthesis of the corresponding 2- (chloroethyl) ammonium chloride is described in PE Aldrich, EC Herrmann, WE Meier, M. Paulshock, WW Prichard, JA Snyder and JC. It can be carried out as described in Watts in J. Med. Chem. 1971, 14, 535-543.

In a second preferred embodiment, the compound of formula (III) is an ω- (alkoxycarbonyl) alkylammonium salt, preferably 2- (C ₁ -C ₄ -alkoxycarbonyl) ethylammonium halide or 3- (C ₁ -C ₄ -alkoxycarbonyl) propylammonium halide. Similarly, in a second preferred embodiment, the compound of formula (III.a) is ω- (alkoxycarbonyl) alkylamine, preferably 2- (C ₁ -C ₄ -alkoxycarbonyl) ethylamine or 3 -(C ₁ -C ₄ -alkoxycarbonyl) propylamine.

In particular, the compound of formula (III) is 2- (C ₁ -C ₄ -alkoxycarbonyl) ethylammonium chloride of formula (III.2) and the compound of formula (III.a) is (III.2 a) 2- (C ₁ -C ₄ -alkoxycarbonyl) ethylamine.

(Where
R ² is selected from alkyl and cycloalkyl, in particular C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, C ₅ -C ₁₅ -cycloalkyl.
R ³ and R ⁴ , R ⁷ and R ⁸ are selected from hydrogen, C ₁ -C ₆ -alkyl and C ₆ -C ₁₀ -aryl. )

Preferably in compounds (III.2) and (III.2.a), R ² is methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclo Selected from dodecyl and 1-adamantyl.

Preferably, in compounds (III.2) and (III.2.a), R ³ and R ⁴ , R ⁷ and R ⁸ are selected from hydrogen and phenyl. In a special embodiment, R ³ and R ⁴ , R ⁷ , R ⁸ are all hydrogen. In certain other special embodiments, one of the groups R ³ and R ⁴ , R ⁷ , R ⁸ is phenyl and the other is hydrogen.

  To synthesize the desired NHC complex, an isonitrile complex of general formula (II) is reacted with a compound of general formula (III) or (III.a).

  This reaction is preferably carried out in the presence of a base, more preferably in the presence of a tertiary amine, particularly triethylamine.

  Suitable reaction temperatures are generally in the range of -10 to 100 ° C, preferably in the range of -0 to 50 ° C. In certain preferred embodiments, the reaction is performed at ambient temperature.

  The process of step a1) of the present invention can be carried out in a suitable solvent that is inert under the respective reaction conditions. Generally suitable solvents are, for example, aromatic compounds such as toluene and xylene, hydrocarbons and hydrocarbon mixtures such as cyclohexane, ethers such as tert-butyl methyl ether and 1,4-dioxane, tetrahydrofuran, methanol and ethanol, Examples thereof include alcohols such as N-propanol, isopropanol, n-butanol and isobutanol, and ketones such as acetone and methyl ethyl ketone.

  In the reaction of the present invention, it is preferable that complete conversion to NHC complex (I) occurs. This reaction can be followed, for example, by shifting the IR stretching frequency of the isonitrile ligand. This method is also effective for the formation of bicyclic NHC complexes using, for example, piperidine or its derivatives as precursors.

Step b1)
A compound of the general formula (I) in which R ³ and R ⁴ are C═O together with the carbon atom to which they are bonded, and the ring carbon atom adjacent to the carbonyl group has a hydrogen atom. Corresponding enol tautomers can be formed as shown in Scheme 4 for I-B.1) and (I-B.2). These tautomers are also included in the present invention.

Scheme 4 (keto-enol tautomer)

In Scheme 4, M and R ¹ , R ² , R ⁶ , R ⁷ and R ⁸ have the above-mentioned meanings, and the meanings described as being particularly preferable.

  The compound capable of enolization of formula (I) obtained in step a) may be subjected to another reaction with a suitable electrophile in step b1).

Thus, a compound of general formula (I) in which R ³ and R ⁴ together with the carbon atom to which they are attached is C═O, for example in the presence of a suitable base, compound R ^3a -Z (formula In which Z is a leaving group). Preferably, Z is selected from halogen ions and tosylate, carboxylate, carbonate, ester, sulfonate, phosphate. Examples of Z are chlorine, bromine, iodine, methanesulfonic acid, trifluoromethanesulfonate, and toluenesulfonic acid, with chlorine and bromine being preferred.

  The base used in step b1) is preferably a non-nucleophilic base, more preferably a hindered alkali amide base such as lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis ( Trimethylsilyl) amide.

  The reaction in step b1) is usually carried out at a temperature in the range of −78 ° C. to atmospheric temperature, preferably at a temperature in the range of −78 to 0 ° C.

Step a2)
In step a2) of the process according to the invention, the isonitrile complex of the general formula (II) is
Amines of formula (V):

(Where
R ² , R ³ and R ⁸ have one of the above meanings and have a particularly preferred meaning;
R ¹⁰ and R ¹¹ have one of the above meanings, preferably R ¹⁰ and R ¹¹ are methyl or ethyl, or R ¹⁰ and R ¹¹ are both 1,2 ethylene or 1,3 propylene groups (its Even if the carbon atom is unsubstituted, or all or a part thereof may be substituted with a methyl group)
Intermediate compounds of formula VI:

(Where
(R ¹ and R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ , M have one of the above-mentioned meanings and have a particularly preferable meaning)
give.

  This reaction is usually carried out in an inert organic solvent. Suitable solvents are halogenated hydrocarbons such as dichloromethane and trichloromethane and ethers such as diisopropyl ether, tert-butyl methyl ether, dioxane, anisole, tetrahydrofuran, dimethoxyethane. This reaction is usually performed at a temperature of 0 ° C to 80 ° C, preferably 10 ° C to 40 ° C.

  The reaction of step a2) can be followed, for example, by shifting the IR stretching frequency of the isonitrile ligand. All yields were good.

In another particular embodiment, the process of step a2) is used to form a compound of formula VI where R ¹ and R ² have different meanings.

In compounds of formula VI, R ¹ is preferably selected from the group of formulas IV.1 to IV.5, and formulas IV.1 and IV.2 are particularly preferred. More preferably, R ¹ is selected from C ₁ -C ₆ -alkyl and phenyl, independently phenyl having 1, 2 or 3 groups selected from C ₁ -C ₆ -alkyl and chlorine. Particularly preferably, R ¹ is selected from tert-butyl, 2,6-dimethylphenyl, 2,4,6 trimethylphenyl, 2,6 diisopropylphenyl, (2-chloro-6-methyl) phenyl.

In the compounds of the formula VI it is preferred that R ² is selected from alkyl and cycloalkyl, in particular selected from C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, C ₅ -C ₁₅ -cycloalkyl It is preferable. In particular, R ² is selected from methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, cyclododecyl, 1-adamantyl.

In the compound of formula VI, it is preferred that R ³ and R ⁸ are independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl.

In the compound of formula VI, it is preferred that R ¹⁰ and R ¹¹ are independently of each other selected from C ₁ -C ₄ -alkyl.

In the compound of formula VI, M is PdCl ₂ (CNR ¹ ), PtCl ₂ (CNR ¹ ), PdCl (CNR ¹ ) ₂ , Au (CNR ¹ ), or AuCl (wherein R ¹ is hydrogen and alkyl, cyclo Preferably selected from alkyl, heterocycloalkyl, aryl, and hetaryl. In particular, M is AuCl.

  The compounds of formula VI are novel compounds and form part of the present invention. They are usually stable to air and moisture and can be stored without decomposition at room temperature.

Step b2)

  In step b2), as shown in Scheme 5, an intermediate compound of formula (VI) is treated with an acid to give compound (VII) having a corresponding carbonyl functional group in the system, and then by intramolecular ring closure, formula I The compound of -E is obtained.

Scheme 5:

In scheme 5, R ¹ and R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ and M have one of the above meanings and have one of the particularly preferred meanings.

  In step i) of scheme 5, compound VI is treated with an acid to give intermediate compound VII, which is further reacted in step II) to give compound IE. Suitable acids are inorganic acids or organic acids. Examples of suitable inorganic acids are mineral acids such as HCl and organic acids such as paratoluene sulfonic acid. Step i) of Scheme 5 is usually performed under hydrolytic conditions. Suitable solvents are those mentioned in step a1).

  The reaction temperature is usually in the range of −10 to 100 ° C., preferably in the range of 0 to 50 ° C.

  Compounds of formula V are obtained as in Scheme 6.

Scheme 6:

In scheme 6, R ¹ and R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ have one of the above meanings and have one of the particularly preferred meanings.

In step i) of Scheme 6, the amine R ¹ —NH ₂ is reacted with a compound of formula (VIII) to give an imine of formula (IX). This reaction is preferably performed in the presence of a dehydrating agent such as magnesium sulfate. This reaction is usually performed in the presence of a solvent. Suitable solvents are halogenated aliphatic hydrocarbons such as dichloromethane, alicyclic or aromatic hydrocarbons. In step II) of scheme 6, the imine compound of formula IX is reduced to give amine compound V. Suitable reducing agents are hydrides such as lithium aluminum hydride or sodium borohydride. This reaction is usually performed in the presence of a solvent. A suitable solvent is a C ₁ -C ₄ -alkanol such as methanol or ethanol.

Step a3)
In the process of the invention, the desired NHC complex of variant a3) represented by formula IF:

(Wherein R ¹ and R ² , R ⁴ , R ⁷ , R ⁸ , M, EWG have one of the above meanings, preferably one of the preferred meanings)
An isonitrile complex of formula IIa is converted to an amine of formula IIIb or IIIc:

(Where
R ² and R ⁴ , R ⁷ and R ⁸ have one of the above meanings,
X ^- is an anion equivalent;
EWG is C (O) R ¹⁴ , C (O) OR ¹⁴ , NO ₂ , S (O) R ¹⁴ or S (O) ₂ R ^{14 where} R ¹⁴ is hydrogen, alkyl, cycloalkyl or aryl It can be produced by reacting with

  This reaction is usually performed in an organic solvent. Suitable organic solvents are aprotic solvents such as haloalkanes, in particular dichloromethane.

  The compound of the general formula (I) of the present invention and / or the compound of the general formula (I) obtained by the method of the present invention can be advantageously used in the NHC metal complex catalytic reaction. This compound of the general formula (I) is preferably used as or in a catalyst used for the reaction of forming a C—C bond, a C—O bond, a C—N bond or a C—H bond. These are used in particular in the C—C coupling reaction selected from Suzuki reaction and Heck reaction, Sonogashira reaction, Stille reaction, Hartwig-Buchwald reaction, and Kumada reaction. They are also used in particular in reactions selected from hydrogenation, hydroformylation, hydrosilylation, Hartwig-Buchwald reaction, and α-arylation of amides. (For CC coupling by cross coupling, SP Nolan and O. Navarro in Comprehensive Organometallic Chemistry III, Vol. 11, 1st ed. (Ed .: A. Canty), Elsevier, Oxford, 2007, Chapter 11.01, 1 -38, and references within; b) F. Glorius, Top. Organomet. Chem. 2007, 21, 1-20; c) EAB Kantchev, CJ O´Brien and MJ Organ, Aldrichimica Acta 2006, 39, 97-111 See

[Suzuki Cross Coupling (Suzuki-Miyaura Cross Coupling)]
A palladium-catalyzed cross-coupling reaction between an organic boron compound and an organic halogen ion or triflate is a method for forming a strong and general carbon-carbon bond.

  The 2010 Nobel Prize in Chemistry was jointly given to A. Suzuki, R. F. Heck and E.i Negishi for their basic achievements in the field of palladium-catalyzed cross-coupling.

Information on the use of NHC metal complexes in the Suzuki reaction can be found in the following literature. a) WA Herrmann, CP Reisinger, M. Spiegler, J. Organomet. Chem. 1998, 557, 93; b) CM Zhang, JK Huang, ML Trudell, SP Nolan, J. Org. Chem. 1999, 64, 3804; c) A. Furstner, A. Leitner, Synlett. 2001, 290; d) CWK Gstottmayr, VPW Bohm, E. Herdtweck, M. Grosche, WA Herrmann, Angew. Chem. Int. Ed. 2002, 41, 1363.
Preferably, the compound of general formula (I) is used in one reaction.

(Where
R ^A is in each case selected from unsubstituted or substituted alkyl and alkenyl, alkynyl, aryl,
R ^b is selected from alkyl, alkoxy and hydroxyl;
R ^C is in each case selected from unsubstituted or substituted alkyl and alkenyl, aryl,
E is selected from Cl and Br, I, CF ₃ SO ₃ , (ORD) ₂ P (═O) O where RD is hydrogen, alkyl, cycloalkyl or aryl;
The base is preferably an alkali metal hydroxide and alkaline earth metal hydroxide, alkali carbonate, alkaline earth metal carbonate, thallium (I) hydroxide, thallium (I) alkanolate, alkali metal phosphate, alkali Selected from metal fluoride. Examples of suitable bases are NaOH and KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , Ba (OH) ₂ , K ₃ PO ₄ , TlOH, thallium (I) ethoxide, KF, CsF, ( C ₄ H ₉ ) ₄ NF, sodium ethoxide, potassium ethoxide, potassium tert-butoxide.

  In particular, the compounds of general formula (I) are used in the following reactions.

  (Wherein cat. Is a catalyst of formula (I))

[Sonogami reaction]
The Sonogashira cross-coupling reaction is a reaction catalyzed by palladium (usually with copper) to give enyne by coupling of a terminal alkyne with an aryl halide or vinyl halide. Information on the use of NHC metal complexes in the Sonogashira reaction can be found in the following literature: a) S. Caddick, FGN Cloke, GKB Clentsmith, PB Hitchcock, D. McKerrecher, LR Titcomb, MRV Williams, J. Organomet. Chem. 2001, 617; b) CL Yang, SP Nolan, Organometallics 2002, 21, 1020; c) L. Ray, S. Barman, MM Shaikh, P. Ghosh, Chem. Eur. J. 2008, 14, 6646.

  Preferably, compounds of general formula (I) are used in certain reactions.

(Where
RE is in each case selected from unsubstituted or substituted alkenyl and aryl, hetaryl,
R ^f is selected from hydrogen and alkyl, alkenyl, aryl, Si (RG) ₃ ,
RG is in each case selected from unsubstituted or substituted alkyl and cycloalkyl, aryl;
E is selected from Cl, Br, I, CF ₃ SO ₃ ,
The base is usually an amine, alkanolate, alkaline earth metal carbonate or alkali metal carbonate. )
This base is preferably selected from secondary alkylamines and tertiary alkylamines, alkali metal alkanolates, and alkali carbonates. This amine compound may be used in excess and also acts as a solvent.

A preferred solvent for the Sonogashira reaction is CH ₃ CN, DMF (dimethylformamide), THF (tetrahydrofuran) or ethyl acetate.

Preferred bases for the Sonogashira reaction are N (C ₂ H ₅ ) ₃ and HN (C ₂ H ₅ ) ₂ , N (iso-C ₃ H ₇ ) ₂ (C ₂ H ₅ ), KO (tert-C ₄ H ₉ ), K ₂ CO ₃ and Cs ₂ CO ₃ .

  In particular, the compound of the general formula (I) is used for the reaction of bromobenzene and 1-hexyne. No other copper source is used.

  Information on the use of NHC metal complexes in the Heck reaction can be found in the following literature: a) WA Herrmann, M. Elison, J. Fischer, C. Kocher, GRJ Artus, Angew. Chem. Int. Ed. 1995, 34, 2371; b) EAB Kantchev, CJ O'Brien, MG Organ, Angew. Chem Int. Ed. 2007, 46, 2768; c) J. Ye, W. Chen, D. Wang, Dalton Trans. 2008, 30, 4015.

  Information on the use of NHC metal complexes in the still reaction can be found in the following literature: G.A. Grasa, S.P. Nolan, Org. Lett. 2001, 3, 119.

  Information on the use of NHC metal complexes in the Kumada reaction can be found in the following literature: V.P.W. Bohm, T. Weskamp, C.W.K. Gstottmayr, W.A. Herrmann, Angew. Chem. Int. Ed. 2000, 39, 1602.

  Information on the use of NHC metal complexes in the Hartwig-Buchwald reaction can be found in the following literature: a) S.R. Stauffer, S.W. Lee, J.P. Stambuli, S.I. Hauck, J.F.Hartwig, Org. Lett. 2000, 2, 1423, b) J. Huang, G. Grasa, S.P. Nolan, Org. Lett. 1999, 1, 1307.

  Information on the use of NHC metal complexes in the α-arylation of amides can be found in the following literature. S. Lee, J.F. Hartwig, J. Org. Chem. 2001, 66, 3402.

  Information on the use of NHC metal complexes in hydrogenation can be found in the following literature: a) HM Lee, T. Jiang, ED Stevens, SP Nolan, Organometallics 2001, 20, 1255; b) LD Vazquez-Serrano, BT Owens, JM Buriak, Chem. Comm. 2002, 2518; c) D. Gnanamgari, ELO Sauer, ND Schley, C. Butler, CD Incarvito, RH Crabtree, Organometallics 2009, 28, 321; d) H. Turkmen, T. Pape, F. Hahn, C. Ekkehardt; Eur. J. Inorg. Chem. 2008, 34, 5418.

  Information on the use of NHC metal complexes in hydroformylation is found in the following literature: J.D. Scholten, J. Dupont, Organometallics 2008, 27, 4439.

  Information on the use of NHC metal complexes in hydrosilylation can be found in the following literature. b) W.A. Herrmann, L.J. Goossen, M. Spiegler, J. Organomet. Chem. 1997, 547, 357.

  The invention is illustrated by the following examples, which are not intended to limit the invention.

[General method]
Unless otherwise noted, all reagents and solvents were from Acros and ABCR, Alpha Acer, Sigma Aldrich or VWR and were used without further purification. Deuterated solvents were purchased from Yurysop. The pure solvent was dried with MB-SPS-800 using a drying column. Production of air and moisture sensitive materials was performed in a nitrogen atmosphere in a flame-dried flask using the Schlenk method. The cross coupling reaction was carried out in an industrial grade solvent. Thin layer chromatography (TLC) was performed using a plastic sheet SIL-G / UV254 (SiO ₂ , thickness: 0.20 mm) coated with polygram (R) from Macherey-Nagel. Column chromatography was performed using silica gel (particle size: 40.0-63.0 nm) manufactured by Machelet Nagel. NMR spectra were recorded on a Bruker Avance 500 spectrometer, a Bruker Avance 300 spectrometer, and a Bruker ARX-250 spectrometer. Chemical shift (unit: ppm) is a value relative to residual solvent protons. The multiplicity of signals was s (singlet), d (doublet), t (triplet), q (quartet) or m (multiplet). ¹³ C assignment was made with DEPT90 and DEPT135 or HSQC-me spectra. MS spectra were recorded with a vacuum generator ZAB-2F, Finigan MAT-TSQ700 or JEOL-JMS-700 spectrometer. GC spectra were recorded on an HP Agilent 5890 Series II plus with an FID analyzer. GC-MS spectra were recorded on an Agilent 5890 Series II plus with an HP5972 mass spectrometer. The IR spectrum (unit: cm ⁻¹ ) was recorded by FT-IR of Bruker Vector 22. Crystal structure analysis was performed with a Bruker Smart CCD or a Bruker APEX diffractometer. Elemental analysis was performed by Elemental Vario EL. React IR (R) analysis was performed on a React IR (R) METTLER TOLEDO IC10.

[Synthesis]
I. Preparation of starting materials
I.0 General synthesis of formamide

R ¹ is as defined above.

  Amine (1) was dissolved in ethyl formate (15 ml), heated in an autoclave at 200 ° C. for 12 hours, and further heated at 250 ° C. for 5 hours. The precipitate was filtered off and washed with n-pentane. Recrystallization from acetone / petroleum ether (1/5) gave the formamide compound (2) as colorless crystals.

I.1 Synthesis of isonitrile ligands
I.1.a General preparation method for isonitrile compounds

R ¹ is as defined above.

Formamide (2) was dissolved in pure dichloromethane. The solution was cooled to −60 ° C. and POCl ₃ was added dropwise over 5 minutes. This suspension was stirred for 20 minutes, and triethylamine was added dropwise over 10 minutes. The resulting yellow suspension was stirred overnight. During this time, the cooling bath was allowed to warm to room temperature.

The suspension was then poured onto ice and allowed to warm to room temperature. Dichloromethane was added and the layers were separated. The organic layer was washed 3 times with saturated aqueous NaHCO ₃ solution. The organic phase was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by distillation or column chromatography (SiO ₂ ).

Example I: 2,4,6-trimethylphenyl isonitrile
2,4,6-Trimethylaniline (10 g, 73.9 mmol) was dissolved in ethyl formate (15 ml). The mixture was heated in an autoclave at 200 ° C. for 12 hours. After this, the solid precipitate was filtered off and washed with pentane. Recrystallization from acetone / petroleum ether (1/3) gave N- (2,4,6-trimethylphenyl) formamide as colorless crystals in almost quantitative yield (11.43 g, 96%). All analytical data are in good agreement with those previously reported (G. Vougioukalakis, J. Am. Chem. Soc. 2008, 130, 2234-2245).

This formamide (1 g, 6.13 mmol) was dissolved in pure dichloromethane (DCM) (30 ml). The solution was cooled to −60 ° C. in an ethanol / liquid nitrogen bath and POCl ₃ (1.67 ml, 18.3 mmol) was added dropwise over 5 minutes. The suspension was stirred for 20 minutes and triethylamine (5.57 g, 55.0 mmol) was added dropwise over 10 minutes. The resulting yellow suspension was stirred overnight. During this time, the cooling bath was allowed to warm to room temperature. The suspension was then poured onto ice and allowed to warm to room temperature. DCM (30 ml) was added and the layers were separated. The organic layer was washed 3 times with saturated aqueous NaHCO ₃ (3 × 10 ml). The organic phase was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by sublimation (50-55 ° C., 6.5 × 10 ⁻² mbar) to give the title compound as colorless crystals (637 mg, 72%). ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 2.23 (s, 3H, -CH ₃ ), 2.31 (s, 6H, -CH ₃ ), 6.95 (s, 2H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 17.19, 19.53, 127.01, 133.16, 137.55 (no other signals observed). All analytical data are in good agreement with those previously reported (G. Vougioukalakis, J. Am. Chem. Soc. 2008, 130, 2234-2245).

Example II: 2,6-Diisopropylphenyl isonitrile
2,6-Diisopropylaniline (purity: 92%, 10 g, 51.9 mmol) was dissolved in elformate (15 ml). The mixture was heated in an autoclave at 200 ° C. for 12 hours and then at 250 ° C. for 5 hours. The solid precipitate was filtered off and washed with pentane. Recrystallization from acetone / petroleum ether (1/5) gave N- (2,6-diisopropylphenyl) formamide as colorless crystals in almost quantitative yield (9.48 g, 46.2 mmol, 89%). . This formamide (1 g, 4.87 mmol) was dissolved in pure DCM (10 ml). The solution was cooled to −60 ° C. in an ethanol / liquid nitrogen bath and POCl ₃ (1.33 ml, 14.6 mmol) was added dropwise over 5 minutes. The suspension was stirred for 20 minutes and triethylamine (4.43 g, 43.8 mmol) was added dropwise over 10 minutes. The resulting yellow suspension was stirred overnight. During this time, the cooling bath was allowed to warm to room temperature. The suspension was then poured onto ice and allowed to warm to room temperature. DCM (30 ml) was added and the layers were separated. The organic layer was washed 3 times with saturated aqueous NaHCO ₃ (3 × 10 ml). The organic phase was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by distillation (72-80 ° C., 4.5 × 10 ⁻² mbar) to give the title compound as a colorless oil (720 mg, 3.84 mmol, 79%). ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.22 (d, 12H, J = 7.0Hz, -CH ₃ ), 3.32 (m, 2H, J = 6.9Hz, -CH-), 7.14 (d , 2H, J = 7.8 Hz, ArH), 7.29 (t, 1H, J = 7.7 Hz, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 23.12, 30.62, 123.94, 130.05, 145.72 ( Other signals are not observed). All analytical data are in good agreement with those previously reported (UJ Kilgore, F. Basuli, JC Huffman, DJ Mindiola, Inorg. Chem. 2006, 45, 487-489).

I.2 Synthesis of isonitrile-Pd complexes General method:
[Pd (CH ₃ CN) ₂ Cl ₂ ] was dissolved in toluene, and 2 equivalents of the above isonitrile were added. The mixture was stirred at room temperature for 12 hours. The precipitate was filtered off, washed with cold pentane and dried under reduced pressure to give the title compound.

Example III: cis- [PdCl ₂ (2,6-dimethylphenyl isonitrile) ₂ ]
[Pd (CH ₃ CN) ₂ Cl ₂ ] (200 mg, 780 μmol) was dissolved in toluene (8 ml) and 2,6-dimethylphenyl isonitrile (212 mg, 1.60 mmol) from Example II was added. The mixture was stirred at ambient temperature for 12 hours. The precipitate was filtered off, washed with cold pentane (3 × 10 ml) and dried under reduced pressure to give the title compound as a white solid (333 mg, 757 μmol, 97%).
IR (KBr): ν = 2363, 2208, 1632, 1473, 1384, 1170, 771, 717, 576, 499, 453; HRMS (FAB ⁺ ) C ₁₈ H ₁₈ N ₂ ClPd [M-Cl ⁻ ] ⁺ : Calculation Value: 403.0193, measured value: 403.0138.

  The following compounds of Examples IV and V, VI, and VII were prepared in the same manner as Example III.

Example IV: cis- [Pd (2,4,6-trimethylphenyl isonitrile) ₂ Cl ₂ ]
The title compound was obtained as a white solid (yield: 89%). IR (KBr): ν = 2919, 2210, 1604, 1471, 1382, 1308, 1035, 853, 712, 600, 568, 502, 473; HR-MS (FAB ⁺ ): calculated value: C ₂₀ H ₂₂ PdClN ₃ [M-Cl ⁻ ] ⁺ = 431.0506, measured value: 431.0486

Example V: cis- [PdCl ₂ (2,6-diisopropylphenyl isonitrile) ₂ ]
The title compound was obtained as a yellow solid (yield: 83%). ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.21 (d, 12H, J = 6.9 Hz, -CH ₃ ), 3.26 (m, 2H, -CH-), 7.17 (d, 2H, J = 7.8 Hz, ArH), 7.40 (t, 1H, J = 7.9 Hz, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 23.24 (q, 8C), 30.78 (d, 4C), 124.77 (d, 6C), 132.52 (s, 4C), 147.24 (s, 2C); IR (KBr): ν = 2966, 2927, 2873, 2209, 1635, 1585, 1475, 1458, 1433, 1388, 1366, 1356 ^{, 1259,1183,1062,800,751,510,477 cm -1; HR-MS} (FAB +): m / z = 515.1140, C 26 H 34 ClN 2 Pd [M-Cl -] + calculated: 515.1145, m / z = 480.1760, C 26 H 34 N 2 Pd [M-Cl -] + calculated: 480.1757.

Example VI: cis- [PdCl ₂ (2-chloro-6-methylphenyl isonitrile) ₂ ]
The title compound was obtained as a white solid (yield: 95%). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 2.45 (s; 3H, CH ₃ ), 7.09 -7.26 (m; 3H, ArH); IR (KBr): ν = 2206, 1632, 1461, 1177, 873 , 782, 711, 569; ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 19.34, 77.43, 127.96, 129.19, 129.59, 131.78, 132.09, 139.68; HRMS (FAB ⁺ ) C ₁₆ H ₁₂ N ₂ Cl ₃ Pd [M-Cl ⁻ ] ⁺ : calculated value 442.9101, measured value: 442.9069

Example VII: cis- [PdCl ₂ (tert-butyl) ₂ ]
The title compound was obtained as a white solid (yield: 92%). All analytical data are in good agreement with those previously reported (S. Otsuka, Y. Tatsuno, K. Ataka, J. Am. Chem. Soc 1971, 93, 6705-6706).

I.3 Synthesis of isonitrile-Au (I) complexes General methods:
1 equivalent of [AuCl (tetrahydrothiophene)] was dissolved in dichloromethane (DCM) and 1 equivalent of isonitrile was added at room temperature. The mixture was stirred for 15 minutes. The solvent was removed under reduced pressure. This crystalline crude product was used without further purification.

Example VIII: [AuCl (2,4,6-trimethylphenyl isonitrile)]
[AuCl (tetrahydrothiophene)] (500 mg, 1.56 mmol) was dissolved in DCM (10 ml) and 2,4,6-trimethylphenyl isonitrile from Example I (233 mg, 1.56 mmol) was added. The mixture was stirred at ambient temperature for 12 hours. After this time, the solvent was removed and the resulting white precipitate was washed with pentane (3 × 10 ml) to give the complex as a white solid (583 mg, 1.54 mmol, 99%). ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 2.28 (s, 6H, CH ₃ ), 2.34 (s, 3H, CH ₃ ), 6.95 (s, 2H, ArH); ¹³ C-NMR (75 MHz , CD ₂ Cl ₂ ): δ = 18.76, 21.59, 129.50, 136.42, 142.30; IR (KBr): ν = 2917, 2207 (-NC), 1602, 1474, 1387, 1308, 1201, 1040, 857, 753, 713, 567, 493; HR-MS (FAB ⁺ ): calculated value: C ₁₀ H ₁₂ AuClN [M + H] ⁺ = 378.0324, measured value: 378.0332.

  The following compounds of Examples IX and X were prepared in the same manner as Example VIII.

Example IX: [AuCl (2,6-diisopropylphenyl isonitrile)]
The title compound was obtained in 99% yield. ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.24 (d, 12H, J = 6.9Hz, CH ₃ ), 3.2 (m, 2H, J = 6.8Hz, -CH-), 7.22 (d, 2H, J = 7.9Hz, ArH) , 7.45 (t, 1H, J = 7.8Hz, ArH); 13 C-NMR (75MHz, CD 2 Cl 2): δ = 22.75 (q, 4C), 30.43 (d, 2C), 124.42 (d, 3C), 132.06 (s, 2C), 146.87 (s); IR (KBr): ν = 2946, 2867, 2208 (NC), 1632, 1462, 1385, 1364, 1261, 1185, 1109, 1062, 936, 799, 750, 534; HR-MS (FAB ⁺ ): calculated value: C ₁₃ H ₁₇ AuN [M-Cl ⁻ ] ⁺ = 384.1027, measured value: 384.1030.

Example X: [AuCl (tert-butylisonitrile)]
The title compound was obtained in 99% yield. All analytical data are in good agreement with those previously reported (R. Heathcote, JAS Howell, N. Jennings, D. Cartlidge, L. Cobden, C. Coles, M. Hursthouse, Dalton Trans. 2007, 13 , 1309-1315).

I.4 Synthesis of isonitrile-Pt (II) complexes General methods:
[Pt (CH ₃ CN) ₂ Cl ₂ ] was dissolved in CHCl ₃ and an appropriate isonitrile was added. The mixture was stirred at reflux for 12 hours. The solvent was removed, and the resulting colorless solid was washed with pentane to obtain an isonitrile-Pt (II) complex.

Example XI: cis- [PtCl ₂ (2,6-diisopropylphenyl isonitrile) ₂ ]
[Pt (CH ₃ CN) ₂ Cl ₂ ] (272 mg, 780 μmol) was dissolved in CHCl ₃ (15 ml) and 2,6-dimethylphenyl isonitrile (212 mg, 1.60 mmol) was added. The mixture was stirred at reflux for 12 hours. The solvent was removed and the resulting colorless solid was washed with pentane (3 × 10 ml) to give the title compound (489 mg, 749 μmol, 96%). ¹ H-NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.25 (d, 12H, J = 6.9 Hz, CH ₃ ), 3.29 (m, 2H, J = 6.9 Hz, -CH-), 7.22 (d, 2H, J = 7.8 Hz, ArH), 7.42 (t, 1H, J = 7.8 Hz, ArH); ¹³ C-NMR (125 MHz, CD ₂ Cl ₂ ): δ = 2.89 (q, 8C), 30.38 (d, 4C), 124.31 (d, 6C), 131.72 (s, 4C), 146.67 (s, 2C); IR (KBr): ν = 2966, 2929, 2869, 2219, 2189, 1475, 1465, 1457, 1436, 1386 , 1365, 1184, 1062, 938, 804, 797, 747, 736, 491 cm ^-1 ; HR-MS (FAB ⁺ ): m / z = 604.2060, calculated value: C ₂₆ H ₃₄ ClN ₂ Pt [M-Cl ^{-] +: 604.2058, m /} z = 569.2372, calculated _{value: C 26 H 34 N 2 Pt} [M-2Cl -] +: 569.2370.

I.5 2- (Chloroethyl) ammonium chloride of general formula III (Y = Cl)

R ² and R ³ , R ⁴ , R ⁷ , R ⁸ have the above meaning, and DCM is dichloromethane.

  The synthesis of 2- (chloroethyl) ammonium chloride is started from commercially available amino alcohols, e.g. A. Habtemariam, B. Watchman, BS Potter, R. Palmer, S. Parsons, A. Parkin, PJ Sadler, J. Chem. Soc., Dalton Trans. 2001, 8, 1306-1318.

I.6 Synthesis of amino alcohols Example XII: 2- (adamantan-1-ylamino) ethanol
1-adamantylamine (1 g, 6.05 mmol) and 2-iodoethanol (1.20 g, 7.00 mmol) were dissolved in benzonitrile (2 ml). The mixture was heated at 120 ° C. for 12 hours. After this time, the precipitate was filtered off and carefully washed with petroleum ether (3 × 20 ml). This white solid was dissolved in DCM (30 ml) and washed with saturated Na ₂ CO ₃ solution (3 × 50 ml). The organic layer was separated, dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure to give the title compound as a colorless oil (950 mg, 4.86 mmol, 80%).

¹ H-NMR (250 MHz, CD ₂ Cl ₂ ): δ = 1.55 (m, 12H, CH ₂ ), 1.99 (OH, NH overlapping with bs, 5H, -CH-), 2.65 (t, 2H, J = 5 Hz , -CH _2- ), 3.44 (t, 2H, J = 5.1Hz, -CH _2- ); all analytical data agree well with those previously reported (e.g., PE Aldrich, EC Herrmann, WE Meier, M. Paulshock, WW Prichard, JA Snyder, JC Watts, J. Med. Chem. 1971, 14, 535-543).

I.7 Preparation of N- (2,2-dimethoxyethyl) amine of general formula V

R ² and R ³ , R ⁸ , R ¹⁰ , R ¹¹ have the above meanings.

In a typical method, 1 equivalent of amine R ² NH ₂ was dissolved in dichloromethane and MgSO ₄ and 1.5 equivalents of compound (4) were added. The mixture was stirred at room temperature for 12 hours. After this, MgSO ₄ was filtered off and the solvent was evaporated. These analytically pure imines were used without further purification. The obtained imine was dissolved in dry methanol and 2 equivalents of NaBH ₄ was added at 0 ° C. The ice bath was removed and the mixture was stirred for an additional 2 hours. The reaction was quenched with water, diluted with dichloromethane, and the organic phase was washed with saturated NH ₄ Cl solution and brine. The crude product was purified by distillation or column chromatography (SiO ₂ ) to give the title compound.

Example XIII: N- (2,2-dimethoxyethyl) -2,4,6-trimethylaniline The title compound was dissolved in 2.50 g (18.5 mmol) of mesitylamine and 3.2 g (27.3 mmol) of 2,2-dimethoxyacetaldehyde ( 60% in water) and 3.00 g MgSO ₄ in 100 ml dichloromethane solution was prepared in a general manner. After filtration of the solvent, N- (2,2-dimethoxyethylidene) -2,4,6-trimethylaniline was obtained as a pale yellow solid; yield: 4.05 g (18.3 mmol, 99%). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 2.07 (s, 6H, CH ₃ ), 2.24 (s, 3H, CH ₃ ), 3.31 (s, 6H, OCH ₃ ), 4.87 (d, J = 4.5 Hz, 1H, CH (OMe) ₂ ), 6.83 (s, 2H, ArH), 7.42 (d, J = 4.5 Hz, 1H, CH = N); ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 18.31 (q, 2C), 20.79 (q), 54.32 (q, 2C), 103.61 (d), 125.82 (d, 2C), 128.87 (s, 2C), 133.52 (s), 147.53 (s), 163.5 (d ); IR (KBr): ν = 3431,2999,2955,2914,2836,1667,1480,1455,1442,1375,1308,1215,1194,1147,1098,1065,1004,983,849,782 cm - ¹ ; HR-MS (EI ⁺ ): m / z = 221.1388, calculated value: C13H19O2N [M] ⁺ : 221.1416.

N- (2,2-dimethoxyethylidene) -2,4,6-trimethylaniline (2.40 g, 10.9 mmol) was dissolved in 50 ml dry methanol under a nitrogen atmosphere and 533 mg NaBH ₄ (14.1 mmol) was added. . After workup, the crude product was purified by distillation (120 ° C., 6 × 10 ⁻² mbar); yield: 2.12 g (mmol, 87.1%); ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 2.27 (s, 3H, CH ₃ ), 2.31 (s, 6H, CH ₃ ), 3.12 (d, J = 6.4Hz, 1H, CH (OMe) ₂ ), 3.26 (bs, NH), 3.44 (s, 6H, OCH ₃ ), 4.51 (t, J = 6.4Hz, 2H, CH ₂ ), 6.86 (s, 2H, ArH); ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 18.27 (q, 2, C), 20.57 (q), 49.73 (t), 53.74 (q, 2C), 103.46 (t), 129.43 (d, 2C), 131.38 (q, 2C), 131.38 (d), 143.05 (s); IR (KBr) : ν = 3379, 2936, 2856, 2832, 1486, 1447, 1376, 1306, 1236, 1194, 1157, 1131, 1074, 1034, 977, 924, 854, 739, 564 cm ^-1 ; HR-MS (EI ⁺ ): m / z = 223.1573, calculated value: C ₁₃ H ₂₁ O ₂ N [M] ⁺ : 223.1572.

I.8 Synthesis of compounds of formula IIIb (EWG = CO (O) CH ₃ )
Example XIV: (E) -Methyl 4- (cyclododecylamino) buteno-2-ate

Under a nitrogen atmosphere, (E) -methyl 4-bromobuteno-2-ate (5.70 g, 31.8 mmol), cyclododecanamine (6.41 g, 35.0 mmol) and Cs ₂ CO ₃ were added to pure tetrahydrofuran (THF) (150.0 ml). ). The mixture was heated under reflux for 12 hours and NH ₄ Cl (saturated solution, 100 ml) was added. The mixture was extracted with DCM (3 times 50.0 ml). The organic layer was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using silica and petroleum ether / ethyl acetate (4: 1) to give the title compound as a yellow solid (5.54 g, 19.7 mmol, 62%). ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.07-1.54 (m, 23H, -CH _2- , -NH-), 2.67 (m, 1H, -CH-), 3.44 (dd, J = _{5.4, 2.2Hz, 2H, -CH 2} -), 3.75 (s, 3H, -CH 3), 6.02 (dd, J = 15.7, 2.1Hz, 1H, = CH-), 7.01 (dq, J = 15.7, 5.2Hz, 1H, = CH-).

II. Synthesis of NHC- (Transition Metal) Complexes of Formula I II.1 Synthesis of NHC- (Transition Metal) Complexes of Formula I-A.2.1 II.1.1 Synthesis of NHC-Pd (II) Complexes
General method for the synthesis of NHC-Pd (II) complex In a typical method, cis- (isonitrile) -Pd (II) complex (321 μmol) and 2- (chloroethyl) ammonium chloride (350 μmol) are suspended in pure THF. Turbid and triethylamine (0.5 ml, 6.81 mmol) was added. The mixture was stirred at ambient temperature for 12 hours. After this time, all of the volatile components were removed under reduced pressure and the solid was dissolved in DCM (20 ml). This solution was extracted with saturated NH ₄ Cl (20 ml). The organic layer was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was dissolved in a minimum amount of DCM and crystallized over a layer of diethyl ether to give NHC-Pd (II) complex as colorless crystals. The crystals were filtered off, washed with diethyl ether and dried under reduced pressure. All the complexes of Examples 1 to 15 listed in Table I are compounds that are stable to air and moisture and can be stored without decomposition at ambient temperature.

Table I

MはPdCl₂(CNR¹)である。

M is PdCl ₂ (CNR ¹ ).

  The physicochemical data for the complexes of Examples 1-14 are shown below.

Example 1:
¹ H-NMR (300 MHz, DMSO): δ = 2.06 (s; 3H, -CH ₃ ), 2.30 (s; 6H, -CH ₃ ), 2.44 (s; 3H, CH ₃ ), 3.52 (s; 3H, _{-CH 3), 3.98 (m;} 4H, -CH 2 -), 7.25 (m; 6H, ArH); 13 C-NMR (75MHz, DMSO): δ = 17.35,17.93,18.68,37.20,51.05,51.20, 128.31, 128.42, 128.93, 129.06, 130.68, 135.33, 135.62, 136.77, 137.71, 182.03; IR (KBr): ν = 3443, 2951, 2919, 2195, 1631, 1541, 1491, 1473, 1411, 1383, 1317, 1276 , 1116, 780, 734, 619; HRMS (FAB ⁺ ) C ₁₉ H ₂₅ N ₃ ClPd [M-Cl ⁻ ] ⁺ : calculated value: 460.00772, measured value: 460.0763.

Example 2:
¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.34 (d, 3H, J = 6.8 Hz, -CH ₃ ), 1.39 (d, 3H, J = 6.7 Hz, -CH ₃ ), 2.01 (s , 3H, -CH ₃ ), 2.27 (s, 6H, -CH ₃ ), 2.47 (s, 3H, -CH ₃ ), 3.82-3.91 (m, 4H, -CH _2- ), 5.40 (m, 1H, J = 6.9, 6.3Hz, -CH-), 6.94 (dd, 1H, J = 7.3, 1.9Hz, ArH), 7.1 (d, 2H, J = 7.6Hz, ArH), 7.17-7.27 (m, 3H, ArH); ¹³ C-NMR (125 MHz, CD ₂ Cl ₂ ): δ = 18.11, 18.92, 19.40, 20.13, 20.93, 43.61, 51.02, 52.25, 128.65, 128.70, 129.62, 130.01, 130.70, 135.64, 136.19, 137.30, 138.70, 184.22; 15N NMR (600 MHz, CD ₂ Cl ₂ , urea): δ = 131.78, 148.43, 171.32; IR (KBr): ν = 2970, 2925, 2358, 2195 (-NC), 1633, 1509, 1467, 1368, 1314, 1271, 1192, 1127, 1102, 1056, 935, 782, 623, 602, 569; HR-MS (FAB ⁺ ): calculated value: C ₂₃ H ₂₉ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 488.1085, found: 488.1104.

Example 3:
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 0.98-1.86 (m, 10H, -CH _2- ), 1.98 (s, 3H, -CH ₃ ), 2.23 (s, 6H, -CH ₃ ) , 2.44 (s, 3H, -CH ₃ ), 3.81 (m, 4H, -CH _2- ), 4.87 (tt, 1H, J = 10.7, 3.8Hz, CH-), 6.9 (dd, 1H, J = 6.6 Hz, ArH), 7.07 (d, 2H, J = 8.4 Hz, ArH), 7.12 (m, 3H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 18.49, 19.23, 19.80, 25.91 , 26.04, 26.12, 31.18, 32.07, 45.24, 51.33, 60.10, 129.02, 129.06, 129.99, 130.38, 131.05, 136.04, 136.57, 139.11, 184.56; IR (KBr): ν = 2931, 2855, 2193 (-NC), 1632, 1510, 1454, 1380, 1333, 1300, 1272, 1170, 1100, 1032, 990, 894, 780, 623, 570; HR-MS (FAB ⁺ ): calculated value: C ₂₆ H ₃₃ ClN ₃ Pd [M -Cl ^{-] +} = 530.1398, measured value: 530.1397.

Example 4:
(Diastereomeric mixture); ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.05-1.81 (m, 10H, CH ₂ ), 1.92 (s, -CH ₃ ), 2.06 (s, -CH ₃ ), 2.17 (s, -CH ₃ ), 2.39 (s, -CH ₃ ), 2.55 (s, CH ₃ ), 4.03 (dd, J = 11.3, 5.6Hz, -CH ₂ ), 4.15 (dd, J = _{11.3, 6.0Hz, -CH 2),} 4.33 (t, J = 11.3Hz, -CH 2), 4.88 (dd, J = 11.8, 5.6Hz, -CH-), 5.03 (dd, J = 11.6, 6.0Hz , -CH-), 5.16 (m, 1H, -CH-), 6.73 (m, 1H, ArH), 6.96-7.32 (m, 10H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 18.27, 18.51, 18.81, 19.08, 19.71, 19.87, 25.10, 25.44, 25.48, 30.24, 30.75, 31.38, 31.77, 50.75, 52.29, 59.58, 59.99, 66.51, 66.56, 77.44, 127.98, 128.01, 128.30, 128.49, 129.07, 129.20, 129.27, 129.57, 129.68, 129.90, 130.36, 130.45, 183.36, 183.98; IR (KBr): ν = 3031, 2932, 2855, 2193, 1631, 1509, 1474, 1453, 1416, 1382, 1296, 1250 , 1210, 1168, 1101, 1034, 998, 780, 701; HR-MS (FAB ⁺ ): calculated value: C ₃₂ H ₃₇ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 604.1711, measured value: 604.1722.

Example 5:
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.32 (d, 3H, J = 6.9Hz, -CH ₃ ), 1.37 (d, 3H, J = 6.6Hz, -CH ₃ ), 1.95 (s , 3H, -CH ₃ ), 2.22 (s, 6H, -CH ₃ ), 2.25 (s, 3H, -CH ₃ ), 2.26 (s, 3H, -CH ₃ ), 2.41 (s, 3H, -CH ₃ ), 3.71-3.92 (m, 4H, -CH _2- ), 5.38 (m, 1H, J = 6.8Hz, -CH-), 6.73 (s, 1H, ArH), 6.90 (s, 2H, ArH), 7.00 (s, 1H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 18.37, 19.14, 19.67, 20.50, 21.27, 21.58, 21.88, 43.86, 51.42, 52.53, 58.95, 129.69, 129.75, 131.02, 135.09, 135.56, 136.25, 138.54, 139.96, 141.77, 184.74; IR (KBr): ν = 2971, 2193, 1608, 1510, 1458, 1382, 1314, 1271, 1197, 1105, 1058, 855, 713, 625 , 599, 573, 460, 428; HR-MS (FAB ⁺ ): Calculated: C ₂₅ H ₃₃ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 516.1398, measured: 516.1391.

Example 6:
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.05 (d, 3H, J = 3.3Hz, -CH ₃ ), 1.07 (d, 3H, J = 3.4Hz, -CH ₃ ), 1.13 (d , 3H, J = 7.0Hz, -CH ₃ ), 1.19 (d, 6H, J = 6.8Hz, -CH ₃ ), 1.21 (d, 6H, J = 6.8Hz, -CH ₃ ), 2.88 (m, 1H , J = 6.8Hz, -CH-), 3.24 (m, 3H, -CH-), 3.71-4.01 (m, 4H, CH2-), 5.47 (dm, 1H, J = 7.0, 6.6Hz, -CH- ), 7.18, 7.17 (dd, 1H, J = 7.7, 1.4Hz, ArH), 7.19 (d, 2H, J = 7.7Hz, ArH), 7.29 (dd, 1H, J = 7.8, 1.7Hz, ArH), 7.40 (m, 2H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 2.65, 21.17, 23.49, 23.63, 23.87, 24.51, 27.22, 27.26, 29.29, 29.54, 30.36, 43.67, 53.03, 124.73, 125.01, 126.19, 130.76, 131.80, 134.57, 146.85, 146.96, 149.31, 185.97; IR (KBr): ν = 2965, 2930, 2870, 2185, 1497, 1459, 1433, 1386, 1366, 1348, 1331, 1315 , 1267, 1184, 1113, 1058, 806, 751, 628; HR-MS (FAB ⁺ ): calculated value: C ₃₁ H ₄₅ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 600.2337, measured value: 600.2335.

Example 7:
¹ H-NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.03 (d, 3H, J = 6.9 Hz, -CH ₃ ), 1.04 (d, 3H, J = 6.9 Hz, -CH ₃ ), 1.11 (d , 3H, J = 6.9Hz, -CH ₃ ), 1.17 (d, 6H, J = 6.8Hz, -CH ₃ ), 1.20 (d, 6H, J = 6.8Hz, -CH ₃ ), 1.34 (d, 3H , J = 6.7Hz, -CH ₃ ), 1.42-1.73 (m, 6H, -CH _2- ), 1.85 (m, 3H, CH2-), 2.86 (m, 1H, J = 6.8Hz, -CH-) , 3.21 (m, 2H, J = 6.9Hz, -CH-), 3.27 (m, 1H, CH-), 4.93 (tt, 1H, J = 11.4, 3.7Hz, -CH-), 7.15 (dd, 1H , J = 7.7, 1.3Hz, ArH), 7.18 (d, 2H, J = 7.9Hz, ArH), 7.28 (dd, 1H, J = 7.8, 1.4Hz, ArH), 7.39 (td, 2H, J = 7.8 , 2.1 Hz, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 20.65, 21.17, 23.49, 23.63, 23.87, 24.51, 27.22, 27.26, 29.29, 29.54, 30.36, 43.69, 53.03, 124.73, 125.01, 126.19, 130.76, 131.80, 134.57, 146.85, 146.96, 149.31, 185.97; IR (KBr): ν = 2963, 2931, 2867, 2188, 1589, 1500, 1458, 1386, 1365, 1336, 1304, 1269, 1184 , 1111, 1055, 804, 750, 731, 626; HR-MS (FAB ⁺ ): calculated value: C ₃₄ H ₄₉ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 640.2650, measured value: 640.2672.

Example 8:
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.0 (d, 3H, J = 6.8 Hz, -CH ₃ ), 1.02 (d, 3H, J = 6.9 Hz, CH ₃ ), 1.07 (d, 3H, _{J = 6.9Hz, -CH 3),} 1.17 (d, 6H, J = 6.9Hz, -CH 3), 1.19 (d, 6H, J = 6.9Hz, -CH 3), 1.4 (d, 3H, J = 6.4Hz, -CH ₃ ), 1.69 (m, 6H, -CH _2- ), 2.23 (m, 3H, -CH-), 2.43 (m, 3H, -CH-, -CH _2- ), 2.74 (m , 3H, -CH-, -CH _2- ), 2.86 (m, 1H, J = 6.8Hz, -CH-), 3.24 (m, 2H, J = 6.8Hz, -CH-), 3.36 (m, 1H , -CH-), 3.66-4.01 (m, 4H, -CH _2- ), 7.06 (dd, 1H, J = 7.7, 1.6Hz, ArH), 7.12 (d, 2H, J = 7.8Hz, ArH), 7.25 (dd, 1H, J = 7.8, 1.8Hz, ArH), 7.33 (td, 2H, J = 7.9, 2.8Hz, ArH); ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 23.09, 23.33, 23.57 , 24.14, 27.01, 27.10, 28.94, 29.16, 29.75, 30.02, 36.12, 42.96, 45.90, 52.74, 59.42, 124.04, 124.06, 125.93, 130.17, 131.02, 135.49, 145.74, 146.333, 148.95, 184.88; IR (KBr): ν = 2965, 2911, 2869, 2186, 1630, 1478, 1456, 1386, 1363, 1330, 1305, 1256, 1190, 1100, 1056, 804, 751, 620; HR-MS (FAB ⁺ ): calculated value: C _{38 H 53 ClN 3 Pd [M} -Cl -] + = 692.2963, Found: 692.2974

Example 9:
(Diastereomeric mixture); ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = -0.14 (d, J = 6.6 Hz, CH ₃ ), -0.06 (d, J = 6.8 Hz, -CH ₃ ) , 0.79 (d, J = 6.8Hz, -CH ₃ ), 1.06-1.99 (m, 29 H), 1.56-3.11 (m, 3H, -CH _2- ), 3.44 (m, J = 6.6Hz, -CH -), 3.87 (dd, J = 11.4, 4.0Hz, -CH _2- ), 4.01 (m, -CH _2- ), 4.36 (m, -CH _2- ), 4.88 (dd, J = 11.2, 4.0Hz , -CH-), 5.11 (m, -CH-), 6.97-7.45 (m, 11H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 22.46, 22.80, 23.54, 23.62, 23.85 , 24.51, 24.73, 25.00, 25.50, 25.58, 25.77, 26.49, 26.79, 26.90, 28.87, 28.96, 29.26, 29.42, 30.01, 30.11, 30.25, 30.81, 31.58, 31.79, 46.15, 52.14, 60.20, 60.68, 68.09, 68.79 , 123.97, 124.27, 124.44, 124.62, 124.98, 125.88, 126.28, 128.09, 128.27, 129.64, 129.75, 129.85, 131.16, 131.47, 133.04, 134.34, 139.45, 140.07, 145.68, 145.78, 146.94, 147.27, 147.70, 67.06, 147.70, 67.06 186.02; IR (KBr): ν = 2943, 2858, 2195, 1631, 1512, 1486, 1473, 1443, 1381, 1354, 1307, 1273, 1253, 1168, 1143, 1096, 1011 ^{779,632; HR-MS (FAB +} ): _{Calculated: C 40 H 53 ClN 3 Pd} [M-Cl -] + = 716.2963, Found: 716.3002.

Example 10:
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.49 (s, 9H, CH ₃ ), 1.71 (s, 9H, CH ₃ ), 3.57 (s, 3H, CH ₃ ), 3.73 (m, 4H, CH ₂ ); ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 30.23, 30.72, 39.22, 47.71, 50.57, 53.64, 56.97, 77.65, 183.1; IR (KBr): ν = 3444, 2980, 2218, 1630, 1530 , 1466, 1371, 1324, 1287, 1200, 1136, 620; HRMS (FAB ⁺ ) C ₁₃ H ₂₄ N ₃ Pd [M-HCl ₂ ] ⁺ : calculated value 328.1011, measured value: 328.1005.

Example 11
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.19 (d, 3H, J = 6.8Hz, -CH ₃ ), 1.26 (d, 3H, J = 6.7Hz, -CH ₃ ), 1.45 (s , 9H, -CH ₃ ), 1.65 (s, 9H, -CH ₃ ), 3.38-3.79 (m, 4H, -CH _2- ), 5.56 (m, 1H, J = 6.7Hz, -CH-); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 18.55, 19.27, 29.01, 29.44, 40.68, 46.02, 52.17, 55.79; IR (KBr): ν = 2979, 2936, 2876, 2217, 1635, 1504, 1454 , 1400, 1369, 1322, 1285, 1235, 1197, 1111, 806, 622, 594, 523; HR-MS (FAB ⁺ ): calculated value: C ₁₅ H ₂₉ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 392.1085 , Measured value: 392.1074.

Example 12:
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 0.98-2.12 (m, 10H, -CH _2- ), 1.45 (s, 9H, -CH ₃ ), 1.66 (s, 9H, -CH ₃ ) , 3.39-3.77 (m, 4H, -CH _2- ), 5.06 (m, 1H, -CH-); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 24.42, 24.53, 29.00, 29.14, 29.45 , 30.07, 41.97, 45.97, 55.83, 59.82, 179.92; IR (KBr): ν = 2918, 2933, 2856, 2216, 1631, 1502, 1451, 1371, 1313, 1283, 1263, 1247, 1225, 1195, 1088, 1031, 804, 622; HR-MS (FAB ⁺ ): Calculated: C ₁₈ H ₃₃ ClN ₃ Pd [M-Cl ⁻ ] ⁺ = 432.1398, measured: 432.1410.

Example 13:
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 2.35 (s, 3H, CH ₃ ), 2.58 (s, 3H, CH ₃ ), 3.66 (s, 3H, CH ₃ ), 4.02 (m, 4H, CH ₂ ), 7.14 (m, 1H, ArH), 7.19 (m, 1H, ArH), 7.27 (m, 2H, ArH), 7.30 (m, 2H, ArH) ppm; ¹³ C-NMR (75 MHz, CDCl ₃ ) : δ = 19.37, 19.75, 38.20, 50.94, 52.10, 77.45, 127.56, 127.74, 129.31, 130.62, 130.99, 131.03, 131.13, 133.06, 135.22, 138.96, 141.41, 186.60; IR (KBr): ν = 3431, 2202, 1632, 1549, 1487, 1458, 1413, 1319, 1273, 1114, 781, 730, 617; HRMS (FAB ⁺ ) C ₁₉ H ₁₉ N ₃ Cl ₃ Pd [M-Cl ⁻ ] ⁺ : Calculated 499.9679, measured : 499.9636.

Example 14
(Diastereomeric mixture); ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 1.45-2.02 (m; 8H, CH ₂ ), 2.01 (s, -CH ₃ ), 2.03 (s, -CH ₃ ), 2.27 (s, -CH ₃ ), 2.29 (s, -CH ₃ ), 2.52 (s, -CH ₃ ), 2.54 (s, CH ₃ ), 3.32 (td, J = 12.7, 3.3Hz, -CH _2- ), 5.07 (m, -CH _2- ), 5.14 (m, -CH _2- ), 6.85-6.91 (m, ArH), 7.08-7.10 (m, ArH), 7.16-7.26 (m, ArH); IR (KBr): ν = 2939, 2856, 2196, 1631, 1519, 1443, 1381, 1307, 1273, 1254, 782, 631, 577; HRMS (FAB ⁺ ) C ₂₄ H ₂₉ N ₃ ClPd [M HCl] ⁺ : Calculated value 500.1085, measured value: 500.1060.

Example 15:
(Diastereomeric mixture, main isomer); ¹ H-NMR (500 MHz, CDCl ₃ ): δ = 0.00 (d, J = 6.6 Hz, 3H, -CH ₃ ), 0.88 (d, J = 6.6 Hz, 3H , -CH ₃ ), 1.09 (d, J = 6.6Hz, 6H, -CH ₃ ), 1.09 (d, J = 6.6Hz, 6H, -CH ₃ ), 1.26 -1.73 (m, 25H, -CH _2- ), 1.59 (d, J = 6.6Hz, 6H, CH ₃ ), 1.68 (m, 2H, -CH _2- ), 1.97 (m, 1H, -CH _2- ), 2.22 (m, 1H, -CH ₂ -), 2.59 (m, J = 6.6Hz, 2H, -CH-), 2.84 (m, J = 6.6Hz, 1H, -CH-), 3.54 (m, 1H, -CH-), 3.83 (m, 1H, -CH _2- ), 4.29 (m, 1H, -CH _2- ), 4.83 (m, 1H, -CH-), 5.24 (m, 1H, -CH-), 6.99 (d, J = 7.7Hz , 1H, ArH), 7.05 (d, J = 7.7Hz, 2H, ArH), 7.17 (d, J = 7.7Hz, 1H, ArH), 7.25-7.33 (m, 5H, ArH), 7.37 (d, J = 6.8 Hz, 2H, ArH); ¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 22.83 (2C), 23.09 (2C), 23.67, 24.60, 25.36 (2C), 26.52, 26.58, 26.72 (2C), 26.94 (2C), 27.07, 27.08, 27.11, 27.22, 27.45 (2C), 28.71, 28.80, 29.65 (2C), 30.83, 32.50, 52.72, 60.84, 68.75, 123.50 (2C), 124.11, 126.06, 128.04 (2C) , 129.54, 129.56 (2C), 129.61, 130.74, 134.22, 139.64, 145.34, 145.51 (2C), 140.34, 186. 39.

II.1.2 Synthesis of NHC-Au (I) complex
General Method for Synthesis of NHC-Au (I) Complex In a typical method, (isonitrile) -Au (I) complex (132 μmol) and 2- (chloroethyl) ammonium chloride (396 μmol) were suspended in pure DCM. . Triethylamine (0.5 ml, 6.81 mmol) was added. The mixture was stirred at ambient temperature for 96 hours. After this time, all volatile components were removed under reduced pressure and the solid was dissolved in DCM (10 ml). This solution was extracted with saturated NH ₄ Cl solution (20 ml). The organic layer was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (SiO _2, mixture of petroleum ether and ethyl acetate; Example 15-18: petroleum ether / ethyl acetate, 2/1; Example 16: petroleum ether / ethyl acetate, 5/1, performed Example 17: Purification with petroleum ether / ethyl acetate, 1/1). All the complexes of Examples 15-18 shown in Table II below are air and moisture stable compounds and can be stored without decomposition at ambient temperature.

Table II

MはAuClである

M is AuCl

  The physicochemical data for the complexes of Examples 16-19 are shown below.

Example 16:
R ^f (petroleum ether / ethyl acetate 2/1) = 0.28; ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.28 (d, 6H, J = 6.8 Hz, -CH ₃ ), 2.17 (s, 6H, -CH ₃ ), 1.26 (s, 3H, -CH ₃ ), 3.72 (s, 4H, -CH _2- ), 4.79 (m, 1H, J = 6.8Hz, -CH-), 6.92 (s, 2H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 17.01, 19.63, 20.09, 42.34, 49.34, 50.89, 128.68, 134.64, 135.19, 138.03, 191.54; IR (KBr): ν = 2968 , 1609, 1506, 1456, 1369, 1344, 1322, 1276, 1263, 1202, 1161, 1099, 1058, 1021, 862, 804, 613, 604, 582; HR-MS (FAB ⁺ ): calculated value: C _{15 H 23 ClN 2 Au [M +} H +] + = 463.1215, Found: 463.1194.

Example 17:
R ^f (petroleum ether / ethyl acetate 5/1) = 0.22; ¹ H-NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.69 (s, 6 H), 2.16 (s, 9 H), 2.26 (s, 3 H), 2.38 (s, 6 H), 3.60 (m, 2H, -CH _2- ), 3.89 (m, 2H, -CH _2- ), 6.92 (s, 2H, ArH); ¹³ C-NMR ( _{75MHz, CD 2 Cl 2):} δ = 18.17,21.27,30.42,36.37,43.75,46.86,49.30,57.43,129.79,136.12,137.20,139.01,192.76; IR (KBr): ν = 2909,2851,1631,1543 , 1494, 1449, 1360, 1312, 1272, 1192, 1142, 1103, 1036, 852, 817, 674, 607, 581.

Example 18:
¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.19 (d, 6H, J = 7.0Hz, -CH ₃ ), 1.29 (d, 12H, J = 6.8Hz, -CH ₃ ), 2.86 (m , 2H, J = 6.9Hz, -CH-), 3.74 (s, 4H, -CH _2- ), 4.81 (m, 1H, J = 6.8Hz, -CH-), 7.19 (d, 2H, J = 7.8 Hz, ArH), 7.38 (m, 1H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 19.67, 23.31, 23.91, 27.72, 42.34, 50.92, 51.98, 123.74, 128.89, 134.09, 146.23 192.18; ¹⁵ N-NMR (600 MHz, CD ₂ Cl ₂ , urea): δ = 130.29, 146.50; IR (KBr): ν = 2964, 2926, 2867, 1631, 1502, 1460, 1385, 1367, 1318, 1274 , 1236, 1192, 1163, 1111, 1059, 1019, 808, 763, 601; HR-MS (FAB ⁺ ): calculated value: C ₁₈ H ₂₉ ClN ₂ Au [M + H ⁺ ] ⁺ = 505.1685, measured value: 505.1652.

Example 19
R ^f (petroleum ether / ethyl acetate 2/1) = 0.18; ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.19 (d, 6H, J = 6.8 Hz; -CH ₃ ), 1.57 (s, 9H, -CH ₃ ), 3.4 (dd, J = 11.4, 8.9Hz, -CH ₂ ), 3.64 (dd, J = 11.4, 8.9Hz, -CH ₂ ), 4.88 (m, J = 6.8Hz, -CH -); ¹³ C-NMR (125 MHz, CD ₂ Cl ₂ ): δ = 20.61, 30.92, 41.92, 47.40, 53.65, 56.06, 191.32; IR (KBr): ν = 2968, 2875, 1494, 1450, 1397, 1366 , 1328, 1282, 1235, 1202, 1117, 955, 711, 676, 610, 521, 436; HR-MS (FAB ⁺ ): calculated value: C ₁₀ H ₂₁ ClN ₂ Au [M + H ⁺ ] ⁺ = 401.1059 , Measured value: 401.1005.

II.1.3 General Method for Synthesis of NHC-Pt (II) Complex In a typical method, cis- (isonitrile) -Pt (II) complex (156 μmol) and 2- (chloroethyl) ammonium chloride (200 μmol) are purified. Suspended in DCM. Triethylamine (0.25 ml, 3.4 mmol) was added. The mixture was stirred at ambient temperature for 72 hours. After this time, all volatile components were removed under reduced pressure and the solid was dissolved in DCM (10 ml). This solution was extracted with saturated NH ₄ Cl solution (20 ml). The organic layer was dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. All the complexes of Examples 19-20 shown in Table III below are air and moisture stable compounds and can be stored without decomposition at ambient temperature.

Table III

MはPtCl₂である。

M is PtCl ₂ .

  The physicochemical data for the complexes of Examples 20 and 21 are shown below.

Example 20
¹ H-NMR (500 MHz, CD ₂ Cl ₂ ): δ = 1.04 (d, 3H, J = 6.7 Hz, -CH ₃ ), 1.06 (d, 3H, J = 6.7 Hz, -CH ₃ ), 1.13 (d , 3H, J = 6.7Hz, -CH 3), 1.19 (d, 6H, J = 6.9Hz, -CH 3), 1.2 (d, 6H, J = 6.9Hz, -CH 3), 1.34 (d, 6H , J = 6.6Hz, CH ₃ ), 1.43 (d, 3H, J = 6.7Hz, -CH ₃ ), 2.88 (m, 1H, J = 6.7Hz, -CH-), 3.24 (m, 3H, -CH -), 3.72-3.98 (m, 4H, -CH _2- ), 5.50 (m, 1H, J = 6.6Hz, -CH-), 7.16 (m, 3H, ArH), 7.27 (d, 1H, J = 7.6 Hz, ArH), 7.39 (m, 2H, ArH); ¹³ C-NMR (125 MHz, CD ₂ Cl ₂ ): δ = 20.24, 20.58, 23.03, 23.11, 23.47, 23.93, 26.74, 26.88, 28.89, 29.23, 29.92, 43.24, 52.24, 124.23, 124.60, 125.63, 130.19, 130.68, 134.68, 146.15, 146.47, 148.62, 173.14; ¹⁹⁵ Pt-NMR (498 MHz, CD ₂ Cl ₂ , Na ₂ PtCl ₄ ): δ = -3669.80; HR -MS (FAB ⁺ ): Calculated: C ₃₁ H ₄₅ Cl ₂ N ₃ Pt [M-Cl ⁻ ] ⁺ = 689.2950, found: 689.2914.

Example 21:
¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ = 1.08 (d, 3H, J = 6.8Hz, -CH ₃ ), 1.10 (d, 3H, J = 6.8Hz, -CH ₃ ), 1.17 (d , 3H, J = 6.8Hz, -CH 3), 1.23 (d, 6H, J = 6.8Hz, -CH 3), 1.25 (d, 6H, J = 6.8Hz, -CH 3), 1.36 (t, 1H , J = 7.3Hz, -CH _2- ), 1.38 (d, 3H, J = 6.8Hz, -CH ₃ ), 1.46-1.58 (m, 3H, -CH _2- ), 1.67 (qd, 1H, J = 12.1, 3.2Hz, CH ₃ ), 1.74 (d, 1H, J = 14.3Hz, CH2-), 1.91 (t, 3H, J = 14.3Hz, -CH _2- ), 2.34 (m, 1H, -CH ₂ -), 2.93 (m, 1H, J = 6.8Hz, -CH-), 3.26 (m, 2H, J = 6.8Hz, -CH-), 3.32 (m, 1H, J = 6.8Hz, -CH-) , 3.79-4.03 (m, 4H, CH2), 5.00-5.06 (m, 1H, CH-), 7.20 (dd, 1H, J = 7.8, 1.4Hz, ArH), 7.22 (d, 2H, J = 7.8, ArH), 7.32 (dd, 1H, J = 7.8, 1.4Hz, ArH), 7.43 (t, 1H, J = 7.8, ArH), 7.44 (t, 1H, J = 7.8, ArH); ¹³ C-NMR ( 150 MHz, CD ₂ Cl ₂ ): δ = 22.81, 22.92, 23.38, 23.75, 25.41, 25.50, 25.68, 26.57, 26.70, 28.70, 29.05, 29.79, 30.55, 31.36, 44.35, 45.99, 59.68, 124.06, 124,30, 124.41, 125.44, 129.98, 130.49, 134.59, 145.93, 146.29, 148.44, 172.84; HR-MS (FAB ⁺ ): calculated value: C ₃₄ H ₄₉ Cl ₂ N ₃ Pt [M-Cl ⁻ ] ⁺ = 729.3263, found: 729.3265.

II.2. Synthesis of NHC- (transition metal) complexes of formula I-B.2.1 II.2.1 Synthesis of Au (I) -NHC complexes General methods:

  Under a nitrogen atmosphere, (tetrahydrothiophene) AuCl (1.00 eq, 50.0 μmol) was dissolved in pure DCM (0.10 M) at ambient temperature. The desired isonitrile (1.05 eq) was added and the solution was stirred for 5 minutes. After this time, the corresponding amine (1.50 equivalents) was added and stirring was continued for 36 hours. The solvent was removed under reduced pressure and the resulting crude product was washed with cold pentane (5 times, 2 ml). The product was dried under reduced pressure. Alternatively, these compounds were purified by column chromatography using a mixture of petroleum ether and ethyl acetate on basic alumina.

Example 22 Chloro (1-cyclohexyl-3- (2,6-diisopropylphenyl) imidazolin-4-one-2-ylidene) gold (I)

¹ H-NMR (500 MHz, CDCl ₃ / C ₆ D ₆ 4/1): δ = 1.08 (d, J = 6.9Hz, 6H, -CH ₃ ), 1.24 (d, J = 6.9Hz, 6H, -CH ₃ ), 1.42 (m, 5H, -CH _2- ), 1.68 (m, 1H, -CH _2- ), 1.82 (m, 2H, -CH _2- ), 1.97 (m, 2H, -CH _2- ) , 2.51 (m, J = 6.9Hz, 2H, -CH-), 3.94 (s, 2H, -CH _2- , carbene main chain), 4.44 (m, 1H, -CH-), 7.16 (d, J = 7.8Hz, 2H, ArH), 7.37 (t, J = 7.8Hz, 1H, ArH); ¹³ C-NMR (125 MHz, CDCl ₃ / C ₆ D ₆ 4/1): δ = 24.26, 24.28, 24.97, 25.10 29.50, 31.99, 48.59, 63.29, 124.73, 129.24, 131.22, 146.29, 171.84, 201.85.

Example 23: Chloro (1-cyclododecyl-3- (2,6-diisopropylphenyl) imidazolin-4-one-2-ylidene) gold (I)

¹ H-NMR (250 MHz, CDCl ₃ ): δ = 1.13 (d, J = 6.9Hz, 6H, -CH ₃ ), 1.21 (d, J = 6.9Hz, 6H, CH ₃ ), 1.18 -1.71 (m, 20H, -CH _2- ), 1.94 (m, 2H, -CH _2- ), 2.57 (m, J = 6.9Hz, 2H, CH-), 4.06 (s, 2H, -CH _2- , carbene main chain) , 4.9 (m, 1H, -CH-), 7.22 (d, J = 7.7Hz, 2H, ArH), 7.44 (t, J = 7.7Hz, 1H, ArH).

Example 24: Chloro (3- (2,6-diisopropylphenyl) -1- (1-phenylethyl) imidazolin-4-one-2-ylidene) gold (I)

¹ H-NMR (250 MHz, CDCl ₃ ): δ = 1.03 (d, J = 6.9 Hz, 3H, -CH ₃ ), 1.10 (d, J = 6.9 Hz, 3H, CH ₃ ), 1.27 (d, J = _{6.9Hz, 2H, -CH 3),} 1.29 (d, J = 6.9Hz, 3H, -CH 3), 1.81 (d, J = 7.2Hz, 3H, -CH 3), 2.43 (m, J = 6.9Hz , 2H, -CH-), 3.65 ( d, J = 21.2Hz, 1H, -CH 2 -, carbene backbone), 4.03 (d, J = 21.2Hz, 1H, -CH 2 -, carbene backbone), 6.06 (q, J = 7.2Hz, 3H, -CH-), 7.2 (m, 8H, ArH).

II.2.2 Synthesis of Pd (II) -NHC Complex General Method for Synthesis of Pd (II) -NHC Complex of Formula I-B.2.1

  In a nitrogen atmosphere, the desired palladium bis (isonitrile) complex (1.00 equivalent, 50.0 μmol) was dissolved in pure THF (0.30 M) at atmospheric temperature. After this, the corresponding amine (1.10 eq) was added and stirring was continued for 7 days. The solvent was removed under reduced pressure and the resulting crude product was washed with cold pentane (5 times, 2.00 ml). The product was dissolved in a minimum amount of DCM and cold pentane was added to precipitate the Pd (II) -NHC complex.

Example 25: Compound of formula I-B.2.1 (R ¹ = 2,6- diisopropyl, R ² = cyclohexyl)

¹ H-NMR (250 MHz, CDCl ₃ ): δ = 0.93 (d, J = 6.8Hz, 3H, -CH ₃ ), 0.96 (d, J = 6.8Hz, 3H, CH ₃ ), 1.04 (d, J = _{6.8Hz, 3H, -CH 3),} 1.19 (d, J = 6.8Hz, 6H, -CH 3), 1.21 (d, J = 6.8Hz, 6H, -CH 3), 1.4 (d, J = 6.8Hz , 3H, -CH ₃ ), 1.10 -2.05 (m, 10H, -CH _2- ), 2.54 (m, 1H, CH-), 3.13 (m, 3H, -CH-), 4.32 (m, 2H, carbene Main chain), 5.22 (m, 1H, -CH-), 7.17 (m, 2H, ArH), 7.44 (m, 4H, ArH).

The title compound was recrystallized from DCM / petroleum ether to give a compound of the formula

II.3. Synthesis of NHC- (Transition Metal) Complexes of Formula I-C.2.1 II.3.1 General Synthesis of Au (I) -NHC Complexes The desired chloroimidazolin-4-one-2-one in a nitrogen atmosphere Iridene) gold (I) complex (50.0 mg, 77.6 μmol, 1 equivalent) was dissolved in pure THF. The mixture was cooled to −78 ° C. and lithium bis (trimethylsilyl) amide (0.14M in THF, 610 μl, 1.1 eq) was added. The mixture was stirred at −78 ° C. for 30 minutes and electrophile (1.1 eq) was added. The mixture was allowed to warm to ambient temperature and stirring was continued for 30 minutes. After this time the solvent was removed and the resulting crude product was washed with pentane (3 times 3 ml). This product was dissolved in pure DCM and filtered through a celite layer to remove LiCl. The solvent was removed under reduced pressure and the resulting solid was stored at −32 ° C. in a nitrogen atmosphere.

Example 26: Chloro (4-((tert-butyldiphenylsilyl) oxy) -1-cyclododecyl-3- (2,6-diisopropylphenyl) -imidazol-2-ylidene) gold (I)

  By the general method described above, the title compound was prepared using tert-butyldiphenylchlorosilane as the electrophile.

¹ H-NMR (250 MHz, CD ₂ Cl ₂ ): δ = 0.85 (s, 9H, -CH ₃ ), 1.09 (d, J = 6.9Hz, 6H, -CH ₃ ), 1.26 (d, J = 6.9Hz , 6H, -CH ₃ ), 0.95-1.79 (m, 22H, -CH _2- ), 2.42 (m, J = 6.9Hz, 2H, CH-), 4.63 (m, J = 6.8Hz, 1H, -CH -), 5.59 (s, 1H, = CH), 7.31 (m, 6H, ArH), 7.45 (m, 7H, ArH).

Example 27: Chloro (4- (benzoyloxy) -1-cyclododecyl-3- (2,6-diisopropylphenyl) -imidazol-2-ylidene) gold (I)

  The title compound was prepared using benzoyl chloride as an electrophile by the general method described above.

¹ H-NMR (250 MHz, C ₆ D ₆ ): δ = 0.98 (d, J = 6.8Hz, 6H, -CH ₃ ), 1.33 (d, J = 6.8Hz, 6H, CH ₃ ), 1.05 -1.92 ( m, 22H, -CH _2- ), 2.62 (m, J = 6.8Hz, 2H, -CH-), 5.17 (m, J = 6.5Hz, 1H, -CH-), 6.76 (t, J = 7.7Hz , 2H, ArH), 6.91 (t, J = 7.5Hz, 1H, ArH), 7.03 (d, J = 7.7Hz, 2H, ArH), 7.19 (m, 2H, ArH, = CH), 7.68 (m, 2H, ArH).

Example 28: Chloro (4-((((4,5-dimethoxy-2-nitrobenzyl) oxy) carbonyl) oxy) -1-cyclododecyl-3- (2,6-diisopropylphenyl) -imidazole-2- Iridene) Gold (I)

  By the general method described above, the title compound was prepared using 4,5-dimethoxy-2-nitrobenzyl chloroformate as an electrophile.

¹ H-NMR (250 MHz, CDCl ₃ ): δ = 1.05 (d, J = 6.8 Hz, 6H, -CH ₃ ), 1.26 (d, J = 6.8 Hz, 6H, CH ₃ ), 1.02 -1.88 (m, 22H, -CH _2- ), 2.32 (m, J = 6.8Hz, 2H, -CH-), 3.83 (s, 3H, CH ₃ ), 3.93 (s, 3H, -CH ₃ ), 5.58 (s, 2H , -CH _2- ), 6.79 (s, 1H, = CH), 7.16 (s, 1H, ArH), 7.2 (d, J = 7.8Hz, 2H, ArH), 7.44 (t, J = 7.8Hz, 1H , ArH), 7.68 (s, 1H, ArH).

III Catalytic Activity of Pd (II) -NHC Complex III.1 General Method for Suzuki-Miyaura Reaction

[Pd] is a Pd catalyst of formula IA.2.1.

There are two methods for this reaction, depending on the phenyl halide used as the substrate.
Method using chlorobenzene as substrate

  Under a nitrogen atmosphere, the Pd (II) -NHC complex [1 mol%] of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 and 2,5 -Dimethylphenylboronic acid (1.20 mmol) and chlorobenzene (1.00 mmol) were dissolved in ethanol (2 ml). The mixture was stirred for 5 minutes and the basic potassium tert-butanolate (1.00 mmol) was added. The solution was stirred for 12 hours. Yield was determined by GC using dodecane (1.00 mmol) as internal standard. The results are summarized in Table IV.

Method using bromobenzene as substrate Pd (II) -NHC complex of Example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 in a nitrogen atmosphere [0.1 mol%], 2,5-dimethylphenylboronic acid (2.40 mmol) and bromobenzene (2.00 mmol) were dissolved in ethanol (4 ml). The mixture was stirred for 5 minutes and the basic potassium tert-butanolate (2.00 mmol) was added. The solution was stirred for 12 hours. Yield was determined by GC using dodecane (1.00 mmol) as internal standard. The results are summarized in Table IV.

III.2 General method of Sonogashira reaction Under a nitrogen atmosphere, the catalyst of Example 15 (2 mol%) was suspended in ethanol (1.00 ml). Bromobenzene (1.00 mmol, 102 μl) and 1-hexyne (1.50 mmol, 173 μl) were added. Finally, KOtBu (1 mmol, solution in 1.00 ml ethanol) was added and the mixture was stirred at ambient temperature for 12 hours. The solvent used was industrial grade ethanol that had not been degassed in advance. This was followed by the addition of ammonium chloride (saturated solution, 2.00 ml), ethyl acetate (4.00 ml) and dodecane (1.00 mmol, 226.2 μl). The organic layer was dried over Na ₂ SO ₄ and analyzed by GC. Yield of hex-1-nylbenzene: 55%.

IV. Synthesis of NHC- (transition metal) complexes of formula IE IV.1. Synthesis route of acyclic gold complexes of formula (VI) a)

R ¹ and R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ have the above meanings.

  In a typical method, 1-2 equivalents of amine (6) was added to a solution of isocyanogold (I) complex (7) in dichloromethane. The mixture was stirred at room temperature for 1-3 days. The solvent was removed under reduced pressure. If necessary, the crude product was purified by column chromatography on silica gel (eluent: dichloromethane).

Route b)
The synthesis of acyclic gold (I) carbene (8) can be carried out in a one-pot method starting from (tetrahydrothiophene) AuCl ((tht) AuCl) in dichloromethane. After the addition of R ¹ -NC, the mixture was stirred at room temperature for 1 hour and then amine (6) was added.

  All complexes are stable to air and moisture and can be stored without decomposition at room temperature.

Example 53: Chloroauric acid ([cyclododecyl (2,2-dimethoxyethyl) amino {[2,6-diisopropylphenyl] amino} methylidene)

The title compound was combined with 100 mg (238 mmol) 2,6-diisopropylphenylisocyanogold (I) chloride and 71.2 mg (250 mmol) N- (2,2-dimethoxyethyl) cyclododecanamine in 5 ml dichloromethane. Used and adjusted in a general way. The reaction mixture was stirred at room temperature for 24 hours and purified by column chromatography to give a colorless crystalline solid; yield: 151 mg (219 mmol, 92%); ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) : δ = 1.18 (d, J = 6.9Hz, 6H, CH ₃ ), 1.24-1.61 (m, 19H), 1.35 (d, J = 6.9Hz, 6H, CH ₃ ), 3.08 (sept, J = 6.9Hz , 2H, CH), 3.47 ( s, 6H, OCH 3), 3.56 (d, J = 4.8Hz, 2H, CH2N), 4.51 (t, J = 4.8Hz, 1H, CH (OCH 3) 2), 7.21 (d, J = 7.4 Hz, 2H, ArH), 7.50 (t, J = 7.4 Hz, 1H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 22.55 (t, 2C), 22.68 (t, 2C), 23.29 (q, 2C), 23.59 (q, 2C), 24.14 (t, 2C), 24.62 (t, 2C), 24.67 (t, 1C), 28.68 (d, 2C), 29.51 ( t, 1C), 48.75 (t, 2C), 53.83 (q, 2C), 64.83 (d, 1C), 105.01 (d, 1C), 124.14 (d, 2H), 129.47 (d, 1C), 135.89 (s , 1C), 146.99 (s, 2C), 198.34 (s, 1C); IR (KBr): ν = 3540, 3268, 2931, 2864, 1592, 1537, 1469, 1445, 1414, 1384, 1362, 1331, 1240 , 1197, 1162, 1119, 1056, 1016, 801, 759 cm ^-1 ; HR-MS (FAB ⁺ ): m / z = 690.3202, calculated value: C ₂₉ H ₅₀ AuClN ₂ O ₂ [M] ⁺ : 690.3226, m / z = 655.350 9. Calculated value: C ₂₉ H ₅₀ AuN ₂ O ₂ [M-Cl ⁻ ] ⁺ : 655.3538.

IV.2 Synthesis of acyclic (palladium or platinum) complexes

M is Pd or Pt;
R ¹ and R ² , R ³ , R ⁸ , R ¹⁰ and R ¹¹ are as defined above.

In a typical method, cis- (isonitrile) ₂ -MeCl ₂ complex (9) and 1 equivalent of amine (6) were stirred in dry THF under nitrogen atmosphere for 2-5 days at room temperature. Complete consumption of the starting material was followed by a shift in the IR stretching frequency of the isonitrile ligand. The solvent was removed under reduced pressure, and the crude product was dissolved in a minimum amount of dichloromethane, covered with a diethyl ether layer and crystallized to obtain an acyclic carbene complex (10) as colorless crystals. The crystals were filtered off, washed with n-pentane or diethyl ether and dried under reduced pressure. This complex is stable to air and moisture and can be stored without decomposition at room temperature.

Example 54

The title compound was prepared according to the typical procedure described above using 70 mg (0.31 mmol) cis- [PdCl ₂ (2,6-diisopropylphenylisonitrile) ₂ and 58.1 mg (0.31 mmol) N- (2,2-dimethoxyethyl). ) Prepared using 8 ml dry THF solution of cyclohexaneamine. Yield: 204 mg (276 mmol, 89%); ¹ H-NMR (500 MHz, CD ₂ Cl ₂ ): δ = 0.93 (d, J = 6.9 Hz, 3H, CH ₃ ), 1.08 (d, J = 6.9 Hz, 3H, CH ₃ ), 1.13 (d, J = 6.9Hz, 3H, CH ₃ ), 1.23 (d, J = 6.9Hz, 6H, CH ₃ ), 1.24 (d, J = 6.9Hz, 6H, CH ₃ ) , 1.52 (d, J = 6.9Hz, 3H, CH ₃ ), 1.52-1.72 (m, 6H), 1.82 (m, 1H), 1.96 (m, 3H), 2.45 (m, 1H), 2.87 (sept, J = 6.9Hz, 1H, CH), 3.06 (sept, J = 6.9Hz, 2H, CH), 3.51 (s, 3H, CH ₃ ), 3.60 (s, 3H, CH ₃ ), 3.71 (d, J = 4.7Hz, 2H, CH ₂ ), 3.88 (sept, J = 6.9Hz, 1H, CH), 4.57 (t, J = 4.7Hz, 1H, CH), 7.11 (m, 1H, ArH), 7.23 (m, 2H, ArH), 7.44 (m, 3H, ArH), 8.71 (bs, 1H, NH); ¹³ C-NMR (500 MHz, CD ₂ Cl ₂ ):; 20.88, 22.56, 22.97 (2C), 23.35 (2C) , 25.63, 25.70, 25.88 (2C), 26.04 (2C), 26.08, 28.84, 29.72, 29.98 (2C), 31.36, 31.60, 50.17, 55.34, 57.01, 68.37, 105.59, 123.05, 124.1, 125.1, 129.77, 131.18, 134.65, 145.85, 146.15 (2C), 149.38, 191.16; IR (KBr): ν = 3447, 3262, 2964, 2932, 2863, 2185, 1665, 1630, 1591, 1543, 1463, 1418, 1386, 1360, 1331, 1142, 1119, 1060, 800, 750 c m ^-1 ; HR-MS (FAB ⁺ ): m / z = 702.3038, calculated value: C ₃₆ H ₅₅ ClN ₃ O ₂ Pd [M-Cl ⁻ ] ⁺ : 702..3028, m / z = 667.3921, calculated _{value: C 36 H 55 N 3 O} 2 Pd [M-Cl -] +: 667.3329.

IV.3 Synthesis of complexes of formula IE In a typical method, the acyclic Au (I) complex (8) and Pd (II) or Pt (II) complex (10) are each dissolved in dichloromethane did. HCl (4N HCl) was added and the mixture was stirred at room temperature for 12 hours. The solvent was removed under reduced pressure. If necessary, the crude product was purified by column chromatography using silica gel (eluent dichloromethane) to give the NHC complex as a crystalline solid in quantitative yield. All complexes are stable to air and water and can be stored without decomposition at room temperature.

Example 55: Chloroauric acid {1-cyclooctyl-3- [2,6-diisopropylyl) phenyl] -1,3-dihydro-2H-imidazol-2-ylidene}

5 mg of 100 mg (0.16 mmol) chloroauric acid ([cyclooctyl (2,2-di-methoxyethyl) amino {[2,6-diisopropylphenyl] amino} methylidene) and 0.25 ml HCl (4N in dioxane) Was stirred at room temperature for 12 hours. The solvent was evaporated to give the title compound as a colorless crystalline solid; yield: 90.0 mg (0.16 mmol,>99%); ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.12 (d , J = 6.9Hz, 6H), 1.28 (d, J = 6.9Hz, 6H), 1.38-1.96 (m, 10H), 2.02-2.18 (m, 4H), 2.33 (sept, J = 6.9Hz, 2H) , 5.01 (quin, J = 6.9Hz, 1H), 6.95 (d, J = 1.9Hz, 1H), 7.24 (d, J = 1.9Hz, 1H), 7.31 (d, J = 7.8Hz, 2H), 7.49 (t, J = 7.8Hz, 1H); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ): δ = 24.54 (q, 2C), 24.62 (q, 2C), 24.91 (t, 2C), 26.35 (t , 1C), 27.22 (t, 2C), 28.97 (d, 2C), 34.78 (t, 2C), 62.72 (d, 1C), 118.27 (d, 1C), 123.94 (d, 1C), 124.66 (d, 2C), 130.91 (d, 1C), 146.48 (s, 2C), 147.07 (s, 1C), 172 (s, 1C); IR (KBr): ν = 3433, 2961, 2925, 1865, 1544, 1471, 1459, 1423, 1411, 1385, 1364, 1307, 1254, 1194, 1120, 1058, 873, 807, 765, 740; HR-MS (FAB ⁺ ): m / z = 570.2086, calculated value: C ₂₃ H ₃₄ AuClN ₂ [M] ⁺ : 570.2076.

IV.4 Synthesis of Formula IF Compound (M = Au-Cl)

R ¹ and R ² , R ⁴ , R ⁷ , R ⁸ , EWG have one of the above-mentioned meanings.

  Method A: Under a nitrogen atmosphere, [AuCl (isonitrile)] (1.00 eq) complex was dissolved in pure DCM and amine (1.50 eq) was added. The mixture was stirred for 48 hours and the solvent was removed under reduced pressure. The resulting solid was washed with petroleum ether to remove residual amine. Alternatively, the crude product could be purified by column chromatography using silica and petroleum ether / ethyl acetate (5: 1) mixture.

  Method B: Under a nitrogen atmosphere, [AuCl (tht)] (1.00 equivalent) (tht = tetrahydrothiophene) was dissolved in pure DCM, and isonitrile (1.00 equivalent) was added. The mixture was stirred at room temperature for 5 minutes and amine (1.50 equiv) was added. The mixture was stirred at room temperature for 48 hours and the solvent was removed under reduced pressure. The resulting solid was washed with petroleum ether to remove residual amine. Alternatively, it could be purified by column chromatography using silica and petroleum ether / ethyl acetate (5: 1) mixture.

Example 56: (1-Cyclododecyl-3- (2,6-diisopropylphenyl) -4- (2-methoxy-2-oxoethyl) -imidazolidin-2-ylidene) gold (I) chloride

Colorless solid, 80.0 mg, 114 μmol, 38%; ¹ H-NMR (301 MHz, CD ₂ Cl ₂ ): δ = 1.17 (d, J = 6.8 Hz, 3H, -CH ₃ ), 1.19 (d, J = 6.8 Hz , 3H, -CH ₃ ), 1.21 (d, J = 6.8Hz, 3H, -CH ₃ ), 1.30 (d, J = 6.8Hz, 3H, -CH ₃ ), 1.14-1.84 (m, 22H, -CH _2- ), 2.67 (m, J = 6.8Hz, 1H, -CH-), 2.92 (m, J = 6.8Hz, 1H, -CH ₃ ), 3.32 (dd, J = 11.5, 10.5Hz, 1H,- CH _2- ), 3.48 (s, 3H, -OCH ₃ ), 3.99 (d, J = 11.2Hz, 1H, -CH _2- ), 4.27 (m, 1H, -CH-), 4.63 (m, 1H, -CH-), 7.15 (m, 2H, ArH), 7.34 (t, J = 7.7Hz, 1H, ArH); ¹³ C-NMR (75 MHz, CD ₂ Cl ₂ ) δ = 22.49 (t), 22.59 (t ), 22.95 (t), 23.24 (t), 23.34 (t), 23.46 (q), 24.10 (q), 24.24 (t), 24.41 (t), 24.66 (t), 24.95 (t), 25.47 (q ), 26.30 (q), 28.62 (t), 28.84 (d), 29.15 (d), 29.25 (t), 37.93 (t), 50.54 (t), 52.36 (q), 55.92 (d), 61.41 (d) ), 124.99 (d), 125.36 (d), 130.30 (d), 133.20 (s), 147.83 (s), 148.34 (s), 170.55 (s), 194.45 (s, carbene carbon atoms).

Example 57: (1-Cyclododecyl-4- (2-methoxy-2-oxoethyl) -3- (2- (trifluoromethyl) phenyl) -imidazolidin-2-ylidene) gold (I) chloride

Colorless solid, 115 mg, 167 μmol, 56%; ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) δ = 1.06-1.83 (m, 22H, -CH _2- ), 2.50 (m, 2H, -CH _2- ), 3.49 (m, 1H, -CH _2- ), 3.52 (s, 3H, -CH ₃ ), 3.90 (t, J = 11.0Hz, 1H, -CH _2- ), 4.55 (m, 1H, -CH-) , 4.64 (m, 1H, -CH-), 7.41 (d, J = 7.7Hz, 1H, ArH), 7.54 (m, 1H, ArH), 7.63 (t, J = 7.7Hz, 1H, ArH), 7.72 (d, J = 7.7Hz, 1H, ArH); IR (KBr) ν = 2935, 2862, 1738, 1605, 1585, 1500, 1459, 1438, 1316, 1266, 1207, 1174, 1130, 1062, 1037, 999 773, 645, 599.

  Example 58: (1-Cyclododecyl-4- (2-methoxy-2-oxoethyl) -3- (naphthalen-2-yl) imidazolidin-2-ylidene) gold (I) chloride

Colorless solid, 149 mg, 223 μmol, 74%; ¹ H-NMR (300 MHz, CD ₂ Cl ₂ ): δ = 1.10-1.87 (m, 22H, —CH ₂ —), 2.45 (dd, J = 16.5, 9.0 Hz, 1H, -CH _2- ), 2.64 (dd, J = 16.5, 4.3Hz, 1H, -CH _2- ), 3.48 (m, 1H, -CH _2- ), 3.50 (s, 3H, -CH ₃ ), 3.97 (t, J = 11.3Hz, 1H, -CH _2- ), 4.71 (m, 1H, -CH-), 4.83 (m, 1H, -CH-), 7.46 (m, 2H, ArH), 7.56 ( m, 1H, ArH), 7.82 (m, 4H, ArH).

Claims (26)

Compounds of general formula (I):

[Where:
n is 0 or 1,
M is a metal atom-containing group,
R ¹ is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl;
R ² is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl [provided that R ¹ and R ² are not both hydrogen],
R ³ and R ⁴ are independently hydrogen, and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, aryl-thio, ( Is selected from (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, and (dihetaryl) amino,
R ³ and R ⁴ together with the carbon atom bonded to them are C═O,
R ³ is an OR ^3a group,
when n = 0, R ⁴ and R ⁷ are bonds corresponding to double bonds between carbon atoms having R ⁴ and R ⁷ , respectively, or
When n = 1, R ⁴ and R ⁵ are bonds corresponding to double bonds between carbon atoms having R ⁴ and R ⁵ respectively.
R ^3a is a group bonded to oxygen via a carbon atom, a silicon atom, a sulfur atom, a phosphorus atom, a boron atom or a titanium atom,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cyclo Alkoxy, cycloalkylthio, (monocycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkyl-thio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl , Aryloxy, arylthio, (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
The two groups R ² and R ⁸ are 3-membered to 12-membered unsubstituted or substituted nitrogen heterocycles with the N atom to which R ² is bonded, optionally independently as O, N, NR ^a [R ^a is hydrogen, alkyl, cycloalkyl or aryl] and one, two or three other heteroatoms or heteroatom-containing groups selected from S forming a nitrogen heterocycle Well,
Or
When n = 0, R ⁴ and R ⁷ may also be a bond corresponding to a double bond between carbon atoms having R ⁴ and R ⁷ ]
A manufacturing method of
a1) Isonitrile complexes of the general formula (II):

[Wherein R ¹ and M represent one of the above meanings],
Compounds of general formula (III) or (IIIa):

[Where:
n, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent one of the above meanings;
X ^- is an anion equivalent,
Y is a leaving group, or
When R ³ and R ⁴ together with the carbon atom bonded to them is C═O, Y is a group OY ^{a wherein} Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, non A substituted or substituted alkylcarbonyl, or an unsubstituted or substituted arylcarbonyl], and
b1) Optionally, when R ³ and R ⁴ together with the carbon atom to which they are attached are C═O, the product obtained in step a1) is compound R ^3a -Z [formula in the presence of a base Wherein Z is a leaving group, and a compound of formula (I) wherein R ³ is an OR ^3a group and when n = 0, R ⁴ and R ⁷ are R ⁴ and A bond corresponding to a double bond between carbon atoms having R ⁷ or, when n = 1, R ⁴ and R ⁵ are bonds corresponding to a double bond between carbon atoms having R ⁴ and R ⁵ Or a step of obtaining
Or
a2) Isonitrile complexes of the general formula II:

[Wherein R ¹ and M represent one of the above meanings] and a compound of the general formula (V):

[Where:
R ² , R ³ and R ⁸ represent one of the above meanings,
R ¹⁰ and R ¹¹ are independently selected from C ₁ -C ₄ -alkyl, or
R ¹⁰ and R ¹¹ together are a linear C ₂ -C ₄ -alkylene optionally substituted with one or more C ₁ -C ₄ -alkyl groups]
Intermediate compound of formula (VI) in reaction with:

[Wherein R ¹ , R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ , and M are as described above]
And
b2) a step of treating the intermediate compound of formula (VI) with an acid (wherein n in compound (I) is 0 and R ⁴ and R ⁷ are double bonds between carbon atoms having R ⁴ and R ⁷⁾ Or a bond corresponding to a bond)
Or
a3) Isonitrile complexes of the general formula II:

[Wherein R ¹ and M represent one of the above-mentioned meanings] and a compound of the general formula (IIIb) or (IIIc):

[Where:
R ² , R ⁴ , R ⁷ , and R ⁸ represent one of the above meanings,
X ^- is an anion equivalent;
EWG is C (O) R ¹⁴ , C (O) OR ¹⁴ , NO ₂ , S (O) R ¹⁴ or S (O) ₂ R ¹⁴ wherein R ¹⁴ is hydrogen, alkyl, cycloalkyl or aryl. [Wherein n is 0 and R ³ is CH ₂ -EWG in compound (I) obtained by modification a3)]
Manufacturing method. In the compound of the general formula (I),
n is 0 or 1,
M is a metal atom-containing group,
R ¹ is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl;
R ² is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl [provided that R ¹ and R ² are not both hydrogen],
R ³ and R ⁴ are independently hydrogen, and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, aryl-thio, ( Is selected from (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, and (dihetaryl) amino,
R ³ and R ⁴ together with the carbon atom bonded to them are C═O,
R ³ is an OR ^3a group,
when n = 0, R ⁴ and R ⁷ are bonds corresponding to double bonds between carbon atoms having R ⁴ and R ⁷ , respectively, or
When n = 1, R ⁴ and R ⁵ are bonds corresponding to double bonds between carbon atoms having R ⁴ and R ⁵ respectively.
R ^3a is a group bonded to oxygen via a carbon atom, a silicon atom, a sulfur atom, a phosphorus atom, a boron atom or a titanium atom,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cyclo Alkoxy, cycloalkylthio, (monocycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkyl-thio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl , Aryloxy, arylthio, (monoaryl) amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino,
The two groups R ² and R ⁸ are 3-membered to 12-membered unsubstituted or substituted nitrogen heterocycles with the N atom to which R ² is bonded, optionally independently as O, N, NR ^a [R ^a is hydrogen, alkyl, cycloalkyl or aryl] and one, two or three other heteroatoms or heteroatom-containing groups selected from S forming a nitrogen heterocycle Good,
A method for producing a compound comprising:
a1) Isonitrile complexes of the general formula (II):

[Wherein R ¹ and M represent one of the above meanings],
Compounds of general formula (III) or (IIIa):

[Where:
n, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent one of the above meanings;
X ^- is an anion equivalent,
Y is a leaving group, or
When R ³ and R ⁴ together with the carbon atom bonded to them is C═O, Y is a group OY ^{a wherein} Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, non A substituted or substituted alkylcarbonyl, or an unsubstituted or substituted arylcarbonyl], and
b1) Optionally, when R ³ and R ⁴ together with the carbon atom to which they are attached are C═O, the product obtained in step a1) is compound R ^3a -Z [formula in the presence of a base Wherein Z is a leaving group, and a compound of formula (I) wherein R ³ is an OR ^3a group and when n = 0, R ⁴ and R ⁷ are R ⁴ and A bond corresponding to a double bond between carbon atoms having R ⁷ or, when n = 1, R ⁴ and R ⁵ are bonds corresponding to a double bond between carbon atoms having R ⁴ and R ⁵ The manufacturing method according to claim 1, further comprising: The production method according to claim 1 or 2, wherein R ¹ and R ² represent different meanings.   The production method according to claim 1 or 2, wherein M is a group containing Pd (II), Pt (II) or Au (I). M is PdCl ₂ (CNR ¹ ), PtCl ₂ (CNR ¹ ), Au (CNR ¹ ), and AuCl, wherein R ¹ is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl The production method according to claim 4, which is selected from: R ¹ is a group of formula IV.1 to IV.5:

[Where:
# Indicates the bond position to the nitrogen atom,
p is 0 or 1,
x is 2 or 3, [wherein x is 2, the carbon atom having the R ⁱ group further has one hydrogen atom],
X _{1 in} formulas IV.2, IV.3, and IV.4 is 0, 1, 2 or 3;
X _{2 in} formulas IV.2, IV.3, and IV.4 is 0 or 1;
[Wherein the sum of x ₁ and x ₂ in formulas IV.2, IV.3 and IV.4 is 0, 1, 2 or 3],
X _{1 in} formula IV.5 is 0, 1 or 2;
X _{2 in} formula IV.5 is 0 or 1;
[Wherein the sum of x ₁ and x ₂ in formula IV.5 is 0, 1 or 2],
When present, A is a C ₁ -C ₁₀ -alkylene group interrupted by one or more non-adjacent groups selected from —O— and S—
Each R ⁱ group is independently
C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -alkyloxy or C ₁ -C ₃₀ -alkylthio [wherein the alkyl chain in alkyl, alkyloxy or alkylthio is interrupted by one or more non-adjacent oxygen atoms It is a group selected from]
The manufacturing method as described in any one of Claims 1-5 represented by these. R ² is selected from alkyl and cycloalkyl, preferably selected from methyl and ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclododecyl, 1-adamantyl Item 7. The production method according to any one of Items 1 to 6. Compounds of general formula (I-A.1) or (I-A.2):

[Where:
M, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent the meanings defined in any one of claims 1 to 7;
R ³ and R ⁴ are independently hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (mono (Cycloalkyl) amino, (dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) ) Amino, (diaryl) amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, (dihetaryl) amino],
A manufacturing method of
a1) Isonitrile complexes of the general formula (II):

[Wherein R ¹ and M represent one of the above meanings],
Compounds of general formula (III) or (IIIa):

[Where:
N, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent one of the above meanings,
X ^- is an anion equivalent,
The manufacturing method as described in any one of Claims 1-7 including reaction with Y is a leaving group. Compound of general formula (I-A.2.1):

[Where:
M, R ¹ , R ² , R ³ , and R ⁷ represent the meanings defined in any one of claims 1 to 7]
The manufacturing method of Claim 8 for manufacturing. The process according to claim 8 or 9, wherein R ³ , R ⁴ , R ⁷ and R ⁸ and, if present, R ⁵ and R ⁶ are all hydrogen. Compounds of general formula (I-B.1) or (I-B.2):

[Where:
M, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the meanings defined in any one of claims 1 to 7],
a1) Isonitrile complexes of the general formula (II):

[Wherein R ¹ and M represent one of the above meanings],
Compounds of general formula (III-B.1), (III-B.1.a), (III-B.2) or (IIIB.2.a):

[Where:
R ² , R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent one of the above meanings,
X ^- is an anion equivalent,
The production method according to any one of claims 1 to 7, comprising a reaction with Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, or unsubstituted or substituted alkylcarbonyl. Compounds of general formula (I-B.2.1):

[Wherein, M, R ¹ and R ² represent the meanings defined in any one of claims 1 to 7]
The manufacturing method of Claim 11 for manufacturing. Compounds of general formula (I-C.1) or (I-C.2):

[Wherein, M, R ¹ , R ² , R ^3a , R ⁶ , R ⁷ , and R ⁸ represent the meanings defined in any one of claims 1 to 7] There,
a1) Isonitrile complexes of the general formula (II):

[Wherein R ¹ and M represent one of the above meanings],
Compounds of general formula (III-C.1), (III-C.1.a), (III-C.2) or (III-C.2.a):

[Where:
R ² , R ⁶ , R ⁷ , and R ⁸ represent one of the above meanings,
X ^- is an anion equivalent,
Y ^a is unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted alkylcarbonyl], and
b1) The method according to any one of claims 1 to 7, comprising a step of further reacting the product obtained in step a1) with compound R ^3a -Z [wherein Z is a leaving group] in the presence of a base. The manufacturing method according to one item. Compounds of general formula (I-C.2.1):

The production method according to claim 13, for producing [wherein M, R ¹ , R ² and R ^3a represent the meanings defined in any one of claims 1 to 7]. R ^3a is the formula VA, VB, VC, VD, VE, VF, VG, VH, VI, VK or VL:

[Where:
# Represents the bonding position to the oxygen atom,
T is selected from -O- and NR ^Vf wherein R ^Vf is hydrogen, alkyl, cycloalkyl or aryl;
R ^Va , R ^Vb , and R ^{Vh are selected from} unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl,
R ^Vc , R ^Vd , and R ^Ve are independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl,
R ^Vg is selected from unsubstituted or substituted heterocycloalkyl,
R ^Vi and R ^Vk are independently of each other an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, an alkoxy unsubstituted or substituted aryloxy, an unsubstituted or substituted cyclo Selected from alkyloxy,
R ^Vm and R ^Vn are independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl. And
R ^Vo and R ^Vp are independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl. And
R ^Vq , R ^Vr and R ^Vs are independently of each other unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted Chosen from hetaryl,
R ^Vt , R ^Vu and R ^Vv are independently of each other unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted Chosen from hetaryl,
R ^Vw , R ^Vx and R ^Vy are independently selected from unsubstituted or substituted alkyloxy, unsubstituted or substituted alkenyloxy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aryloxy And
The method according to claim 13 or 14, wherein D ⁺ is a group selected from the group consisting of cation equivalents.   The process according to any one of claims 1 to 15, wherein the reaction in step a1) is carried out in the presence of a base, preferably in the presence of a base selected from tertiary amines.   The process according to any one of claims 1 to 16, wherein the reaction of step b1) is carried out in the presence of a base, preferably in the presence of a non-nucleophilic base, in particular lithium bis (trimethylsilyl) amide. Compounds of general formula (IE):

A process for producing [wherein M and R ¹ , R ² , R ³ , R ⁸ represent the meanings defined in any one of claims 1 to 7],
a2) Isonitrile complexes of the general formula II:

[Wherein R ¹ and M represent one of the above meanings],
Compound of general formula (V):

[Where:
R ² , R ³ and R ⁸ represent one of the above meanings,
R ¹⁰ and R ¹¹ are independently selected from C ₁ -C ₄ -alkyl, or R ¹⁰ and R ^{11 taken} together may be substituted with one or more C ₁ -C ₄ -alkyl groups. Reaction with good linear C ₂ -C ₄ -alkylene]
Intermediate compound of formula (VI):

[Wherein R ¹ , R ² , R ³ , R ⁸ , R ¹⁰ , R ¹¹ , and M are as defined above],
and
b2) treating the intermediate compound of formula (VI) with an acid;
The manufacturing method as described in any one of Claims 1-7 containing these. Compounds of general formula (IF):

Wherein R ¹ , R ² , R ⁴ , R ⁷ , R ⁸ , M, and EWG are as defined above, comprising:
a3) Isonitrile complexes of the general formula II:

[Wherein R ¹ and M are as defined above],
Compounds of general formula (IIIb) or (IIIc):

[Where:
X ^- is an anion equivalent;
R ² , R ⁴ , R ⁷ , R ⁸ , and EWG are as defined above]
The manufacturing method as described in any one of Claims 1-7 including reaction with these.   20. A method according to claim 18 or 19, wherein M is AuCl.   Compounds of general formula (I) as defined in any of claims 1 to 15 and 18 to 20.   Catalyst comprising or consisting of a compound of general formula (I) as defined in any of claims 1 to 15 and 18 to 20.   A catalyst used as or in a catalyst used in the reaction of forming a CC bond, CO bond, CN bond or CH bond of a compound of general formula (I) as defined in any of claims 1-15 and 18-20 Usage in.   24. The method of using according to claim 23 in a CC coupling reaction selected from Suzuki reaction, Heck reaction, Sonogashira reaction, Stille reaction, and Kumada reaction.   24. Use according to claim 23 in a reaction selected from hydrogenation and hydroformylation, hydrosilylation, Hartwig-Buchwald reaction, α-arylation of amides. Compound of general formula (VI):

[Where:
R ¹ is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl;
R ² is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and hetaryl [provided that R ¹ and R ² are not both hydrogen],
R ³ is hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl) amino, ( (Dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) amino, (diaryl) Amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, and (dihetaryl) amino;
R ⁸ is hydrogen and, in each case, unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl) amino, (dialkyl) amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl) amino, ( (Dicycloalkyl) amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl) amino, (diheterocycloalkyl) amino, aryl, aryloxy, arylthio, (monoaryl) amino, (diaryl) Amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl) amino, and (dihetaryl) amino,
The two groups R ² and R ⁸ are 3-membered to 12-membered unsubstituted or substituted nitrogen heterocycles with the N atom to which R ² is bonded, optionally independently as O, N, NR ^a [R ^a is hydrogen, alkyl, cycloalkyl or aryl] and one, two or three other heteroatoms or heteroatom-containing groups selected from S to form a nitrogen heterocycle. Well,
R ¹⁰ and R ¹¹ are independently selected from C ₁ -C ₄ -alkyl, or R ¹⁰ and R ^{11 taken} together may be substituted with one or more C ₁ -C ₄ -alkyl groups. Good linear C ₂ -C ₄ -alkylene; and
M is a metal atom-containing group].