DE19629523A1 - Optically active compound preparation by intramolecular Stetter reaction - Google Patents
Optically active compound preparation by intramolecular Stetter reactionInfo
- Publication number
- DE19629523A1 DE19629523A1 DE1996129523 DE19629523A DE19629523A1 DE 19629523 A1 DE19629523 A1 DE 19629523A1 DE 1996129523 DE1996129523 DE 1996129523 DE 19629523 A DE19629523 A DE 19629523A DE 19629523 A1 DE19629523 A1 DE 19629523A1
- Authority
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- Germany
- Prior art keywords
- aryl
- compound
- stetter
- intramolecular
- chiral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 238000007296 Stetter synthesis reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 5
- GCGFIFNQFLLJIR-UHFFFAOYSA-N 5-bromo-1-methylindole-2-carboxylic acid Chemical compound BrC1=CC=C2N(C)C(C(O)=O)=CC2=C1 GCGFIFNQFLLJIR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims abstract 3
- 239000012442 inert solvent Substances 0.000 claims abstract 2
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 125000001425 triazolyl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- 150000003254 radicals Chemical class 0.000 claims 3
- 150000005840 aryl radicals Chemical class 0.000 claims 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 125000004953 trihalomethyl group Chemical group 0.000 claims 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 abstract 1
- 125000005110 aryl thio group Chemical group 0.000 abstract 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 230000001419 dependent effect Effects 0.000 abstract 1
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 5
- UDALHVUWSFOPSC-QPJJXVBHSA-N methyl (e)-4-(2-formylphenoxy)but-2-enoate Chemical compound COC(=O)\C=C\COC1=CC=CC=C1C=O UDALHVUWSFOPSC-QPJJXVBHSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- FGNLEIGUMSBZQP-UHFFFAOYSA-N cadaverine dihydrochloride Chemical compound Cl.Cl.NCCCCCN FGNLEIGUMSBZQP-UHFFFAOYSA-N 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PKQWJSMHKMTJBK-UHFFFAOYSA-N 4-(2-formylphenoxy)but-2-enoic acid Chemical compound OC(=O)C=CCOc1ccccc1C=O PKQWJSMHKMTJBK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ICZHJFWIOPYQCA-OAHLLOKOSA-N (1r)-1-anthracen-9-yl-2,2,2-trifluoroethanol Chemical compound C1=CC=C2C([C@@H](O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 ICZHJFWIOPYQCA-OAHLLOKOSA-N 0.000 description 1
- ZOPKCXNPYUFUFY-UHFFFAOYSA-N 2-(4-oxo-2,3-dihydrochromen-3-yl)acetic acid Chemical compound C1=CC=C2C(=O)C(CC(=O)O)COC2=C1 ZOPKCXNPYUFUFY-UHFFFAOYSA-N 0.000 description 1
- -1 4,5-dihydro-1H-1,2,4-triazol-5-ylidenes Chemical class 0.000 description 1
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical class C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UDALHVUWSFOPSC-UHFFFAOYSA-N methyl 4-(2-formylphenoxy)but-2-enoate Chemical class COC(=O)C=CCOC1=CC=CC=C1C=O UDALHVUWSFOPSC-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Unter Stetter-Reaktion versteht man die Addition eines Aldehyds an eine Doppelbindung, die mindestens durch einen elektronenziehenden Substituent (Z) aktiviert ist.Stetter reaction is the addition of an aldehyde to a double bond, the is activated by at least one electron-withdrawing substituent (Z).
Die Stetter-Reaktion wird entweder durch Cyanidionen (Übersicht H. Stetter, H. Kuhlmann, Org. React. (1991) 40, 407-496) oder durch Thiazoliumylide (generiert in situ aus Thiazoliumsalze und Basen) katalysiert (H. Stetter, H. Kuhlmann, Chem. Ber. (1976) 109, 2890; H. Stetter, Skobel, Chem. Ber. (1987) 120, 643).The Stetter reaction is either caused by cyanide ions (overview H. Stetter, H. Kuhlmann, Org. React. (1991) 40, 407-496) or by thiazoliumylides (generated in situ from thiazolium salts and Bases) catalyzed (H. Stetter, H. Kuhlmann, Chem. Ber. (1976) 109, 2890; H. Stetter, Skobel, Chem. Ber. (1987) 120, 643).
Es sind nur wenige Beispiele bekannt für intramolekulare Stetter-Reaktionen:Only a few examples of intramolecular Stetter reactions are known:
B. Trost, C. D. Shuey, F. DiNinno, C. D. McElvain, J. Am. Chem. Soc. (1979) 101, 1284B. Trost, C. D. Shuey, F. DiNinno, C. D. McElvain, J. Am. Chem. Soc. (1979) 101, 1284
E. Ciganek, Synthesis (1995) 1311.E. Ciganek, Synthesis (1995) 1311.
Es sind keine Beispiele für enantioselektive, intramolekulare Stetter-Reaktionen in der Literatur beschrieben.There are no examples of enantioselective, intramolecular Stetter reactions in the Literature described.
Der Erfindung liegt die Aufgabe zugrunde, bei intramolekularen Stetter-Reaktionen Enantioselektivität zu erzielen.The invention has for its object in intramolecular Stetter reactions Achieve enantioselectivity.
Überraschenderweise wurde gefunden, daß diese Aufgabe mit Hilfe bestimmter Katalysatoren lösbar ist, die chirale Substituenten aufweisen. Triazoliumcarbene (4,5-Dihydro-1H-1,2,4-triazol-5-ylidene, Formel I) mit chiralen Substituenten sind hervorragende Katalysatoren für intramolekulare, enantioselektive Stetter-Reaktionen. Diese Triazoliumcarbene können entweder isoliert oder in situ erzeugt werden (z. B. durch Deprotonierung des entsprechenden Triazoliumsalzes II oder durch a-Eliminierung von HY aus den Triazolinen III),Surprisingly, it has been found that this task can be done with the help of certain Solvable catalysts that have chiral substituents. Triazolium carbenes (4,5-dihydro-1H-1,2,4-triazol-5-ylidenes, formula I) with chiral Substituents are excellent catalysts for intramolecular, enantioselective Stetter reactions. These triazolium carbenes can either be isolated or generated in situ (e.g. by deprotonation of the corresponding triazolium salt II or by a-elimination of HY from the triazolines III),
worin R₁ und R₃ für Alkyl oder Aryl stehen können (R₂ und R₃ können auch zu einem Ring
verknüpft sein),
R₂ für Alkyl, Aryl, H, ein Halogenatom, Perfluoralkyl, Alkoxy, Phenoxy, R- bzw.
Aryl-S, R₂N, Cyano und Nitro steht,
Y für Alkoxy, Phenoxy, Aryl-S, R₂-N, Cyano, Trihalomethan, etc. steht und X ein Anion
ist. Derartige Katalysatoren hat die Anmelderin bereits in P 196 09 074.1 für die
Herstellung von optisch aktiven Hydroxyketonen beschrieben.wherein R₁ and R₃ can be alkyl or aryl (R₂ and R₃ can also be linked to form a ring),
R₂ represents alkyl, aryl, H, a halogen atom, perfluoroalkyl, alkoxy, phenoxy, R- or aryl-S, R₂N, cyano and nitro,
Y represents alkoxy, phenoxy, aryl-S, R₂-N, cyano, trihalomethane, etc. and X is an anion. The applicant has already described such catalysts in P 196 09 074.1 for the production of optically active hydroxyketones.
In den vorstehend genannten Substituentenbedeutungen hat der Alkylrest oder der Alkylteil eines Restes vorzugsweise 1-8 C-Atome, insbesondere 1-6 C-Atome und ist vorzugsweise chiral. Der Alkylrest kann auch durch einen Phenylrest substituiert sein. Reste dieses Typs sind z. B. der Benzyl- oder der Phenylethylrest.In the substituent meanings mentioned above, the alkyl radical or the alkyl part has a residue is preferably 1-8 C atoms, in particular 1-6 C atoms and is preferred chiral. The alkyl radical can also be substituted by a phenyl radical. Remains of this type are z. B. the benzyl or phenylethyl radical.
Aryl steht vorzugsweise für Phenyl.Aryl is preferably phenyl.
Halogen bedeutet vorzugsweise Cl oder Br.Halogen is preferably Cl or Br.
Katalysatoren vom Typ I-III, bei denen R₁, R₃ oder beide chirale Reste sind, katalysieren intramolekulare Stetter-Reaktionen unter Bildung eines neuen Stereozentrums in guter Ausbeute mit guter Enantioselektivität (z. B. ee 41-71%).Type I-III catalysts in which R₁, R₃ or both are chiral radicals catalyze intramolecular Stetter reactions to form a new stereo center in good Yield with good enantioselectivity (e.g. ee 41-71%).
Dies sei am Beispiel der schon oben erwähnten Zyklisierung von 4-(2-Formylphenoxy)-2-butenoat (IV) zu (4-Chromanon-3-yl)essigsäureester (V) gezeigt.This is the example of the cyclization of 4- (2-formylphenoxy) -2-butenoate mentioned above (IV) to (4-chromanon-3-yl) acetic acid ester (V).
Verbindungen vom Typ Y sind wichtig als Ausgangsprodukte für viele biologisch aktive Verbindungen (z. B. Pflanzenschutzmittel), wie z. B. Pterocarpane. Siehe dazu folgende Literaturstellen: Y. Ozaki, L Mochida, S.-W Kirn, J. Chem. Soc. Perkin Trans. 1 (1989) 1219; M. Davis, M. Pettett, D. Scanlon, Y. Feriito, Austr. J. Chem. (1977) 30, 2289; J. L. Ingham, Progress in the Chemistry of Organic Natural Products, Eds. W. Herz, H. Grisebach, G. W. Kirby, Springer Verlag, Wien-New York, 1983, Vol. 43, p. 15 und 121.Type Y compounds are important as starting materials for many biologically active Compounds (e.g. pesticides) such as B. Pterocarpane. See the following References: Y. Ozaki, L Mochida, S.-W Kirn, J. Chem. Soc. Perkin Trans. 1 (1989) 1219; M. Davis, M. Pettett, D. Scanlon, Y. Feriito, Austr. J. Chem. (1977) 30, 2289; J.L. Ingham, Progress in the Chemistry of Organic Natural Products, Eds. W. Herz, H. Grisebach, G. W. Kirby, Springer Verlag, Vienna-New York, 1983, vol. 43, p. 15 and 121.
Als Katalysator verwendet man eine Verbindung der Formel VI:A compound of formula VI is used as catalyst:
worin R₁ für Phenyl,
R₃ für (4S,5S)-2,2-dimethyl-4-phenyl-1,3-dioxan-5-yl und
R₂ für H stehen.wherein R₁ is phenyl,
R₃ for (4S, 5S) -2,2-dimethyl-4-phenyl-1,3-dioxan-5-yl and
R₂ stand for H.
Zu einer gerührten Lösung von 1.25 mmol 4-(2-Formylphenoxy)-2-butenoat (IV) und 0.118 g (0.25 mmol) von VI in 40 ml trockenem Tetrahydrofuran wurden 0.0175 g K₂CO₃ bei Raum temperatur zugegeben. Nach 24 Stunden wurde das Reaktionsgemisch mit Wasser versetzt, mit Dichlormethan extrahiert und die organische Phase über Natriumsulfat getrocknet. Das Lösungsmittel wurde im Vakuum entfernt und der Rückstand durch Flash-Chromatographie (Silikagel, Diethylether/Pentan 1 : 1) gereinigt. Die 4-Chromanone wurden als kristalline, farblose Feststoffe oder als hellgelbe Öle isoliert. Die Ergebnisse sind in der folgenden Tabelle zusammengefaßt.To a stirred solution of 1.25 mmol 4- (2-formylphenoxy) -2-butenoate (IV) and 0.118 g (0.25 mmol) of VI in 40 ml of dry tetrahydrofuran were 0.0175 g of K₂CO₃ in the room temperature added. After 24 hours, water was added to the reaction mixture, with Extracted dichloromethane and dried the organic phase over sodium sulfate. The Solvent was removed in vacuo and the residue by flash chromatography (Silica gel, diethyl ether / pentane 1: 1). The 4-chromanones were as crystalline, colorless Solids or isolated as light yellow oils. The results are in the table below summarized.
[a] Die Position der Substituenten wurde nach der für chromanone üblichen Numerierung angegeben. [b] Die Enantiomerenüberschüsse wurden entweder mittels HPLC mit einer chiralen Stationärphase (Chiralcel OD (Daicel) oder (S,S)-Whelk-01) oder mittels NMR Shiftexperimenten mit (R)-(-)-1-(9-Anthryl)-2,2,2-trifluorethanol als chirales Cosolvens bestimmt. [c] Die absolute Konfiguration von 3a wurde anhand der chemischen Verschiebungen der Mosher-Derivate im NMR ermittelt. Alle anderen wurden durch Analogie deduziert. [d] Nach 48 Stunden mit 50 mol% Katalysator. Die Werte in Klammern wurden nach 24 Stunden mit 20 mol% Katalysator erreicht. [e] Nach 14 Stunden mit 10 mol% Katalysator. Die Werte in Klammern wurden nach 14 Stunden mit 20 mol% Katalysator erreicht. [f] Phenylring an den Positionen 5 und 6 des Chromanones aneliert.[a] The position of the substituents was determined according to the numbering used for chromanones specified. [b] The enantiomeric excesses were determined either by HPLC with a chiral Stationary phase (Chiralcel OD (Daicel) or (S, S) -Whelk-01) or using NMR shift experiments determined with (R) - (-) - 1- (9-anthryl) -2,2,2-trifluoroethanol as a chiral cosolvent. [c] The absolute Configuration of 3a was based on the chemical shifts of the Mosher derivatives in NMR determined. All others were deduced by analogy. [d] After 48 hours with 50 mol% catalyst. The values in brackets were after 24 hours with 20 mol% catalyst reached. [e] After 14 hours with 10 mol% catalyst. The values in brackets were after 14 Hours achieved with 20 mol% catalyst. [f] Phenyl ring at positions 5 and 6 of the Chromanones fused.
Zu einer gerührten Lösung von 0.275 g (1.25 mmol) 4-(2-Formylphenoxy)-2-butensäuremethyl ester (IV) und der angegebene Menge Katalysator in 40 ml trockenem Tetrahydrofuran wurden 0.5 mol K₂CO₃ pro Mol Katalysator bei Raumtemperatur zugegeben. Nach der angegebenen Reaktionszeit wurde das Reaktionsgemisch mit Wasser versetzt, mit Dichlormethan extrahiert und die organische Phase über Natriumsulfat getrocknet. Das Lösungsmittel wurde im Vakuum entfernt und der Rückstand durch Flash-Chromatographie (Silikagel, Diethylether/Pentan 1 : 1) gereinigt. Die Ergebnisse sind in der folgenden Tabelle zusammengefaßt.To a stirred solution of 0.275 g (1.25 mmol) of 4- (2-formylphenoxy) -2-butenoic acid methyl ester (IV) and the specified amount of catalyst in 40 ml of dry tetrahydrofuran 0.5 mol K₂CO₃ per mol of catalyst added at room temperature. After the specified Reaction time, the reaction mixture was mixed with water, extracted with dichloromethane and the organic phase dried over sodium sulfate. The solvent was removed in vacuo removed and the residue by flash chromatography (silica gel, diethyl ether / pentane 1: 1) cleaned. The results are summarized in the following table.
Zu einer gerührten Lösung von 0.275 g (1.25 mmol) 4-(2-Formylphenoxy)-2-butensäuremethyl ester (IV) und 0.25 mmol des Thiazoliumsalzes in 40 ml trockenem Tetrahydrofuran wurden 0.25 mol Triethylamin bei Raumtemperatur zugegeben. Nach 24 h wurde das Reaktionsgemisch mit Wasser versetzt, mit Dichlormethan extrahiert und die organische Phase über Natriumsulfat getrocknet. Das Lösungsmittel wurde im Vakuum entfernt und der Rückstand durch Flash-Chromatographie (Silikagel, Diethylether/Pentan 1 : 1) gereinigt. Das gewünschte Chromanon wurde mit 13% Ausbeute aber nur 7% e.e. isoliert.To a stirred solution of 0.275 g (1.25 mmol) of 4- (2-formylphenoxy) -2-butenoic acid methyl esters (IV) and 0.25 mmol of the thiazolium salt in 40 ml of dry tetrahydrofuran were 0.25 mol of triethylamine added at room temperature. After 24 h, the reaction mixture was with Water added, extracted with dichloromethane and the organic phase over sodium sulfate dried. The solvent was removed in vacuo and the residue through Flash chromatography (silica gel, diethyl ether / pentane 1: 1) cleaned. The desired chromanon was obtained in 13% yield but only 7% e.e. isolated.
Claims (6)
R₁ und R₃ jeweils für einen Alkyl- oder Arylrest stehen, von denen mindestens einer chiral ist und
R₂ für Alkyl, Aryl, H, ein Halogenatom, Perfluoralkyl, Alkoxy, Phenoxy, Aryl-S, R₂N, Cyano oder Nitro steht.1. A process for the preparation of optically active compounds by intramolecular Stetter reaction, wherein a compound having an aldehyde function and an activated CC double bond, which is arranged so that it can react intramolecularly with the aldehyde function, in an inert solvent with brings a Stetter reaction catalyst into contact, characterized in that a chiral compound of the general formula I used where
R₁ and R₃ each represent an alkyl or aryl radical, at least one of which is chiral and
R₂ represents alkyl, aryl, H, a halogen atom, perfluoroalkyl, alkoxy, phenoxy, aryl-S, R₂N, cyano or nitro.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996129523 DE19629523A1 (en) | 1996-07-22 | 1996-07-22 | Optically active compound preparation by intramolecular Stetter reaction |
| DE19731200A DE19731200A1 (en) | 1996-07-22 | 1997-07-21 | Preparing optically active compound by intramolecular Stetter reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996129523 DE19629523A1 (en) | 1996-07-22 | 1996-07-22 | Optically active compound preparation by intramolecular Stetter reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19629523A1 true DE19629523A1 (en) | 1998-01-29 |
Family
ID=7800489
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1996129523 Withdrawn DE19629523A1 (en) | 1996-07-22 | 1996-07-22 | Optically active compound preparation by intramolecular Stetter reaction |
| DE19731200A Withdrawn DE19731200A1 (en) | 1996-07-22 | 1997-07-21 | Preparing optically active compound by intramolecular Stetter reaction |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19731200A Withdrawn DE19731200A1 (en) | 1996-07-22 | 1997-07-21 | Preparing optically active compound by intramolecular Stetter reaction |
Country Status (1)
| Country | Link |
|---|---|
| DE (2) | DE19629523A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000039063A1 (en) * | 1998-12-25 | 2000-07-06 | Chisso Corporation | Liquid crystal compounds exhibiting negative anisotropy of permittivity |
| US6426419B1 (en) | 1999-03-31 | 2002-07-30 | California Institute Of Technology | Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity |
-
1996
- 1996-07-22 DE DE1996129523 patent/DE19629523A1/en not_active Withdrawn
-
1997
- 1997-07-21 DE DE19731200A patent/DE19731200A1/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000039063A1 (en) * | 1998-12-25 | 2000-07-06 | Chisso Corporation | Liquid crystal compounds exhibiting negative anisotropy of permittivity |
| US6576303B1 (en) | 1998-12-25 | 2003-06-10 | Chisso Corporation | Liquid crystal compounds exhibiting negative anisotropy of permittivity |
| DE19982965B3 (en) * | 1998-12-25 | 2012-08-30 | Jnc Corporation | Liquid crystalline compound with a negative value of dielectric anisotropy |
| US6426419B1 (en) | 1999-03-31 | 2002-07-30 | California Institute Of Technology | Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity |
| US6624265B2 (en) | 1999-03-31 | 2003-09-23 | California Institute Of Technology | Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19731200A1 (en) | 1998-02-12 |
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