CN106905162B - A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene - Google Patents
A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene Download PDFInfo
- Publication number
- CN106905162B CN106905162B CN201710029566.0A CN201710029566A CN106905162B CN 106905162 B CN106905162 B CN 106905162B CN 201710029566 A CN201710029566 A CN 201710029566A CN 106905162 B CN106905162 B CN 106905162B
- Authority
- CN
- China
- Prior art keywords
- nitro
- benzyloxymethyl
- formylcyclohexene
- aryl
- preparation
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 9
- -1 nitro, amino Chemical group 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- ANSYAMHYCYOWAW-UHFFFAOYSA-N 3-phenylmethoxypropanal Chemical compound O=CCCOCC1=CC=CC=C1 ANSYAMHYCYOWAW-UHFFFAOYSA-N 0.000 claims abstract 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 150000003335 secondary amines Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 229960001701 chloroform Drugs 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- RPMXALUWKZHYOV-UHFFFAOYSA-N nitroethene Chemical group [O-][N+](=O)C=C RPMXALUWKZHYOV-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 238000005057 refrigeration Methods 0.000 abstract description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种3‑苄氧甲基‑4‑芳香基‑5‑硝基‑1‑甲酰基环己烯的制备方法，所述3‑苄氧甲基‑4‑芳香基‑5‑硝基‑1‑甲酰基环己烯结构通式如I所示：式中R为一取代、二取代、三取代和四取代的卤素、硝基、氨基、1‑10碳烷基或1‑10烷氧基；制备方法包括如下：将3‑苄氧基丙醛、(E)‑(2‑硝基乙烯)芳香化合物与二级胺和溶剂混合，于0～25℃反应1‑24小时后，经洗涤、萃取、分离，得到3‑苄氧甲基‑4‑芳香基‑5‑硝基‑1‑甲酰基环己烯；本发明提供的合成方法操作简单、反应条件温和，不需要无水、无氧处理，也不需要低温制冷。目标产物收率高，所得目标产物的为单一异构体，在光学纯催化剂催化下反应的对映选择性大于99％ee。The present invention relates to a preparation method of 3-benzyloxymethyl-4-aryl-5-nitro-1-formylcyclohexene, wherein the 3-benzyloxymethyl-4-aryl-5-nitro The general structural formula of base-1-formylcyclohexene is shown in I: In the formula, R is a halogen, nitro, amino, 1-10 carbon alkyl or 1-10 alkoxy which is monosubstituted, disubstituted, trisubstituted and tetrasubstituted; the preparation method includes the following: 3-benzyloxy propionaldehyde , (E)-(2-nitroethylene) aromatic compound is mixed with secondary amine and solvent, reacted at 0～25 ℃ for 1-24 hours, washed, extracted and separated to obtain 3-benzyloxymethyl-4 -aryl-5-nitro-1-formylcyclohexene; The synthesis method provided by the invention is simple in operation, mild in reaction conditions, does not require anhydrous and oxygen-free treatment, and does not require low-temperature refrigeration. The yield of the target product is high, the obtained target product is a single isomer, and the enantioselectivity of the reaction under the catalysis of an optically pure catalyst is greater than 99% ee.
Description
Technical field
The present invention relates to a kind of preparation methods of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene, belong to
In compound synthesis technical field.
Background technique
Polysubstituted hexamethylene olefine aldehydr be widely present in the structure of biologically active natural products and drug.They are also
Very useful organic synthesis intermediate.Its newest synthetic method is to synthesize such complexity by the more meters of Lip rivers reaction of organic catalysis
Structure.Enders etc. is more by three components that secondary amine is catalyzed alpha, beta-unsaturated aldehyde, nitro compds hydrocarbon compound and simple aldehyde
The reaction of rice Lip river has synthesized three substitutions and quaternary hexamethylene olefine aldehydr (Adv.Synth.Catal.2008,350,267-279)；Gong
Three substitutions have been synthesized Deng reacting by secondary amine catalysis simple alcohols, crotonaldehyde with more meters of Lip rivers of four components of nitro compds hydrocarbon compound
Hexamethylene olefine aldehydr (Chem.Eur.J.2009,15,6815-6818)；Chen etc. is catalyzed alpha, beta-unsaturated aldehyde and 2- by secondary amine
The α of nitro allyl acetate, γ-regioselectivity [3+3] cycloaddition reaction synthesize such polysubstituted hexamethylene olefine aldehydr
(Org.Lett.2016,18,116-119)。
However, the disadvantages of these synthetic method yields are not high, and the reaction time is long, and some reaction raw materials are complicated, this nothing
It doubts and limits its application.
Summary of the invention
It is an object of the invention to solve the deficiencies in the prior art, a kind of 3- benzyloxymethyl -4- aromatic radical -5- nitre is provided
The preparation method of base -1- formyl cyclohexene.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene,
3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formoxyl cyclohexene the general formula is as shown in I:
R is a substitution, two substitutions, three substitutions and quaternary halogen, nitro, amino, 1-10 carbon alkyl or 1-10 alcoxyl in formula
Base；
Preparation method include the following: by 3- benzyloxy propionic aldehyde, (E)-(2- nitroethylene) aromatic compound and secondary amine and
Solvent mixing, it is washed, extract, separate in 0~25 DEG C after reaction 1-24 hour, obtain 3- benzyloxymethyl -4- aromatic radical -5-
Nitro -1- formyl cyclohexene；
Preferably, the mol ratio of 3- benzyloxy propionic aldehyde and (E)-(2- nitroethylene) aromatic compound is 2~5:1；
Secondary amine is α, the α-diphenylprolinol that racemization, R configuration and S configuration oxygen are trimethyl silane protection, respectively such as
Shown in formula C1, C2 and C3, dosage is the 1~100% of (E)-(2- nitroethylene) aromatic compound mole dosage；
Organic solvent is methylene chloride, chloroform, ether, tetrahydrofuran, toluene, ethyl alcohol, n-hexane, petroleum ether or different
Propyl alcohol, consumption of organic solvent are 3~20 times of substrate total weight, and reaction temperature is -20 DEG C~40 DEG C,
Preferably, secondary amine dosage is 1~30%, the You Jirong of (E)-(2- nitroethylene) aromatic compound mole dosage
Agent dosage is 3~10 times of substrate total weight.
Preferably, the 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene is individual isomer.
The beneficial effects of the present invention are: synthetic method provided by the invention is easy to operate, reaction condition is mild, nothing is not needed
Water, anaerobic processing, do not need cryogenic refrigeration yet.Target product yield is high, and gained target product is individual isomer, in optics
The enantioselectivity reacted under pure catalyst is greater than 99%ee.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
Technical solution of the present invention described in detail below.The embodiment of the present invention only for illustrating specific method, this method its
Scale should not be limited by the examples.
Embodiment 1:3- benzyloxymethyl -4- phenyl -5- nitro -1- formyl cyclohexene
3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol), (E)-(2- nitroethylene) benzene are added in 100mL reaction flask
(29.8mg, 0.2mmol), catalyst C1 (13mg, 0.04mmol) and 10mL n-hexane are placed in 0 DEG C and stir 24 hours, TLC inspection
Survey fully reacting.Reaction solution concentration rear pillar chromatography (leacheate: petrol ether/ethyl acetate=10/1 to 5/1) obtains target production
Object 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene 53mg, yield 75%.
Embodiment 2:(3S, 4S, 5S) -3- benzyloxymethyl -4- phenyl -5- nitro -1- formyl cyclohexene
Method similar to Example 1: in 100mL reaction flask be added 3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol),
(E)-(2- nitroethylene) benzene (29.8mg, 0.2mmol), catalyst C2 (13mg, 0.04mmol) and 10mL n-hexane, are placed in 0
DEG C stirring 24 hours, TLC detect fully reacting.Reaction solution is concentrated rear pillar and chromatographs (leacheate: petrol ether/ethyl acetate=10/1
To 5/1) obtain target product (3S, 4S, 5S) -3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene
53.5mg, yield 76%, > 99%ee.
Embodiment 3:(3R, 4R, 5R) -3- benzyloxymethyl -4- phenyl -5- nitro -1- formyl cyclohexene
Method similar to Example 1: in 100mL reaction flask be added 3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol),
(E)-(2- nitroethylene) benzene (29.8mg, 0.2mmol), catalyst C3 (13mg, 0.04mmol) and 10mL n-hexane, are placed in 0
DEG C stirring 24 hours, TLC detect fully reacting.Reaction solution is concentrated rear pillar and chromatographs (leacheate: petrol ether/ethyl acetate=10/1
To 5/1) obtain target product (3R, 4R, 5R) -3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene
53.4mg, yield 76%, > 99%ee.
Embodiment 4:(3S, 4S, 5S) -3- benzyloxymethyl -4- (p-fluorophenyl) -5- nitro -1- formyl cyclohexene
Method similar to Example 1: in 100mL reaction flask be added 3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol),
(E) the fluoro- 4- of -1- (2- nitroethylene) benzene (33.4mg, 0.2mmol), catalyst C2 (13mg, 0.04mmol) and 10mL just oneself
Alkane is placed in 0 DEG C and stirs 24 hours, and TLC detects fully reacting.Reaction solution is concentrated rear pillar and chromatographs (leacheate: petroleum ether/acetic acid second
Ester=10/1 to 5/1) obtain target product (3S, 4S, 5S) -3- benzyloxymethyl -4- (p-fluorophenyl) -5- nitro -1- formyl
Cyclohexene 57.6mg, yield 78%, > 99%ee.
Embodiment 5:(3S, 4S, 5S) -3- benzyloxymethyl -4- (rubigan) -5- nitro -1- formyl cyclohexene
Method similar to Example 1: in 100mL reaction flask be added 3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol),
(E) the chloro- 4- of -1- (2- nitroethylene) benzene (36.7mg, 0.2mmol), catalyst C2 (13mg, 0.04mmol) and 10mL just oneself
Alkane is placed in 0 DEG C and stirs 24 hours, and TLC detects fully reacting.Reaction solution is concentrated rear pillar and chromatographs (leacheate: petroleum ether/acetic acid second
Ester=10/1 to 5/1) obtain target product (3S, 4S, 5S) -3- benzyloxymethyl -4- (rubigan) -5- nitro -1- formyl
Cyclohexene 56.3mg, yield 73%, > 99%ee.
Embodiment 6:(3S, 4S, 5S) -3- benzyloxymethyl -4- (aminomethyl phenyl) -5- nitro -1- formyl cyclohexene
Method similar to Example 1: in 100mL reaction flask be added 3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol),
(E) -1- methyl -3- (2- nitroethylene) benzene (32.6mg, 0.2mmol), catalyst C2 (13mg, 0.04mmol) and 10mL just oneself
Alkane is placed in 0 DEG C and stirs 24 hours, and TLC detects fully reacting.Reaction solution is concentrated rear pillar and chromatographs (leacheate: petroleum ether/acetic acid second
Ester=10/1 to 5/1) obtain target product (3S, 4S, 5S) -3- benzyloxymethyl -4- (aminomethyl phenyl) -5- nitro -1- first
Acyl group cyclohexene 51.2mg, yield 70%, > 99%ee.
Embodiment 7:(3S, 4S, 5S) -3- benzyloxymethyl -4- (m-bromophenyl) -5- nitro -1- formyl cyclohexene
Method similar to Example 1: in 100mL reaction flask be added 3- benzyloxy propionic aldehyde (82.1mg, 0.5mmol),
(E) the bromo- 3- of -1- (2- nitroethylene) benzene (45.6mg, 0.2mmol), catalyst C2 (13mg, 0.04mmol) and 10mL just oneself
Alkane is placed in 0 DEG C and stirs 24 hours, and TLC detects fully reacting.Reaction solution is concentrated rear pillar and chromatographs (leacheate: petroleum ether/acetic acid second
Ester=10/1 to 5/1) obtain target product (3S, 4S, 5S) -3- benzyloxymethyl -4- (m-bromophenyl) -5- nitro -1- formyl
Cyclohexene 57.6mg, yield 67%, > 99%ee.
The present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only in order to illustrate this hair
Bright principle, without departing from the spirit and scope of the present invention, the present invention also have the variation of various unsubstantialities and change
Into these both fall in the scope of protection of present invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710029566.0A CN106905162B (en) | 2017-01-16 | 2017-01-16 | A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710029566.0A CN106905162B (en) | 2017-01-16 | 2017-01-16 | A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106905162A CN106905162A (en) | 2017-06-30 |
| CN106905162B true CN106905162B (en) | 2019-03-05 |
Family
ID=59207301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710029566.0A Active CN106905162B (en) | 2017-01-16 | 2017-01-16 | A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106905162B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173946A (en) * | 2021-04-16 | 2021-07-27 | 西安国睿新药安全评价研究中心有限公司 | Synthesis and application of polyfunctional group cyclohexene aldehyde compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501980B2 (en) * | 2008-05-30 | 2013-08-06 | Sumitomo Chemical Company, Ltd. | Process for producing oseltamivir phosphate and intermediate compound |
-
2017
- 2017-01-16 CN CN201710029566.0A patent/CN106905162B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106905162A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2020022507A (en) | Biosynthesis of cannabinoids | |
| US8329931B2 (en) | Organoaluminum compound | |
| Okamoto | Synthetic Reactions Using Low‐valent Titanium Reagents Derived from Ti (OR) 4 or CpTiX3 (X= O‐i‐Pr or Cl) in the Presence of Me3SiCl and Mg | |
| CN103333942A (en) | A synthetic method for (R)-praziquantel | |
| CN106905162B (en) | A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene | |
| CN102718768B (en) | Chiral five-membered bicyclic guanidine compound, preparation method and application thereof | |
| CN111072605B (en) | A kind of preparation method of fluoroalkyl substituted benzofuran derivative or indole derivative | |
| CN100478333C (en) | Chiral and non-chiral diimidazolinylbenzene compounds and synthesis method | |
| CN101260085A (en) | A method for the synthesis of chiral gamma-sultam by catalytic asymmetric hydrogenation | |
| CN102153477A (en) | Novel method for synthesizing chiral 4-nitryl-3, 5-diaryl cyclohexanone | |
| JP6028606B2 (en) | Method for producing amine compound | |
| CN101628904B (en) | Synthesis method of 2-nitro-3-aryl-2,3,5,7-tetrahydrobenzofuran-4-one derivative | |
| CN105566242B (en) | The preparation method of Linezolid and its intermediate | |
| Huang et al. | Asymmetric synthesis of ceramide sphingolipid based on (2S, 3S, 4S)-3, 4-dihydroxy-5-(hydroxymethyl) pyrrolidine lactam | |
| Tanaka et al. | Catalytic dehydrogenative N-((triisopropylsilyl) oxy) carbonyl (Tsoc) protection of amines using iPr 3 SiH and CO 2 | |
| Yu et al. | Highly efficient asymmetric vinylogous Mannich reaction induced by O-pivaloylated D-galactosylamine as the chiral auxiliary | |
| JP6015494B2 (en) | Method for producing alkylene polyamine | |
| CN107892655B (en) | A method for preparing 4-aminobutyrate derivatives | |
| CN100545155C (en) | Synthetic method of paclitaxel and docetaxel side chains and derivatives thereof | |
| Massolo et al. | 2-Carboxythioester-1, 3-dithiane: A Functionalized Masked Carbonyl Nucleophile for the Organocatalytic Enantioselective Michael Addition to Enones | |
| Wiedemann et al. | Functionalized aminocyclopropanes from functionalized organozinc compounds and N, N-dialkylcarboxamides | |
| CN114773382B (en) | Chiral compound alpha-siloxylketone derivative containing indole/carbazole skeleton, preparation method and application | |
| CN114621986B (en) | Method for biosynthesis of taxol side chain | |
| CN115677674B (en) | A method for preparing a heterocyclic compound containing indole ketone and 3-acylbenzofuran or indole structure | |
| CN117447356B (en) | A cyclopentenone derivative, its synthesis method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190725 Address after: 310000 Room 311, Building No. 688, Bin'an Road, Changhe Street, Binjiang District, Hangzhou City, Zhejiang Province Patentee after: Hangzhou Li'an Biological Technology Co., Ltd. Address before: 324000 North Road, Quzhou, Zhejiang, No. 78, No. nine Patentee before: Quzhou University |
|
| TR01 | Transfer of patent right |