CN106365956A - Method of alcoholization of D-carvone and separation of enantiomer - Google Patents
Method of alcoholization of D-carvone and separation of enantiomer Download PDFInfo
- Publication number
- CN106365956A CN106365956A CN201610801075.9A CN201610801075A CN106365956A CN 106365956 A CN106365956 A CN 106365956A CN 201610801075 A CN201610801075 A CN 201610801075A CN 106365956 A CN106365956 A CN 106365956A
- Authority
- CN
- China
- Prior art keywords
- compound
- methyl
- alcohol
- cyclohexene
- carvone
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
- C12P41/003—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions
- C12P41/005—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions by esterification of carboxylic acid groups in the enantiomers or the inverse reaction
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
Abstract
The invention discloses a method of reduction alcoholization of D-carvone and resolution of an enantiomer by biocatalysis. The D-carvone is taken as a raw material and subjected to reduction with sodium borohydride to obtain a compound II, the compound II is subjected to enzymatic kinetic resolution reaction to obtain a compound III and a compound IV, or the compound II is subjected to dynamic kinetic resolution to obtain the compound III of which the yield is higher than 90%, and a compound V can be obtained by hydrolyzing the compound III. The method further changes a prochiral ketone group in the D-carvone into a chiral hydroxyl center and carries out further resolution; and the method has the characteristics of simplicity of operation, high yield of product, good optical purity and the like.
Description
Technical field
The present invention relates to a kind of preparation method of optical homochiral hydroxy compound, especially derived with d- carvone for raw material
Preparation (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol simultaneously carries out detached method to its enantiomer.
Background technology
The reduction method for alcoholizing of the d- carvone of report is, with d- carvone under the reduction of zinc borohydride, to be prepared into
Arrive (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol (regioselective reduction of
epoxides and conjugated carbonyl compounds using zeolite supported zinc
Borohydride, tetrahedron letters, 39 (29), 5151-5154;1998) zinc borohydride, is used as also
Former dose, eventually because having zinc ion easily to form precipitation in system, and more intractable.
And optical isomer (1s, the 5s) -2- first of (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol is usually then with d- carvone as raw material, not right by living things catalysis
Reduction reaction is claimed to obtain (an enzymatic toolbox for cascade reactions:a showcase for an
In vivo redox sequence in asymmetric synthesis, chemcatchem, 5 (12), 3524-3528;
2013;engineering rieske non-heme iron oxygenases for the asymmetric
Dihydroxylation of alkenes, angewandte chemie, international edition, 54 (44),
12952-12956;2015);(1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol is similarly to use
Asymmetric reduction reaction obtains (non-natural elemane as the " stepping stone " for the
Synthesis of germacrane and guaiane sesquiterpenes, organic letters, 15 (1),
152-155;2013).
With regard to (1s, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol and (1r, 5s) -2- methyl -
In the preparation method of 5- (1- methyl ethylene) -2- cyclohexene -1- alcohol, the method for enzymatic kinetic resolution then there is not yet
Arrive.
Content of the invention
In order to study to d- carvone further, the present invention, with d- carvone as raw material, its prochiral ketone group is carried out
Further reaction obtains chiral hydroxyl group neutrality, further splits, obtains the compound of optically pure hydroxyl.Implemented
Journey is as follows:
1) under condition of ice bath, with alcohol as solvent, add raw material d- carvone, sodium borohydride by a certain percentage, then keep low temperature
Under the conditions of reacted, obtain compound, i.e. (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol;
2) in organic solvent toluene, with step 1) gained compound as raw material, by a certain percentage add acry radical donor, fat
Enzyme, carries out kinetic resolution reaction at a certain temperature, obtains compound, i.e. (1r, 5s) -2- methyl -5- (1- methyl second
Thiazolinyl) -2- cyclohexene -1- alcohol acyl compounds;And compound, i.e. (1s, 5s) -2- methyl -5- (1- ethylene methacrylic
Base) -2- cyclohexene -1- alcohol;After reaction terminates, filter, concentrate, crossing column purification respectively to pure compound and compound
ⅳ;
3) in organic solvent toluene, with step 1) gained compound, add acry radical donor, Digestive Enzyme by a certain percentage, disappear
Rotation catalyst carries out Dynamic Kinetic Resolution reaction at a certain temperature, compound can be fully converted to compound,
The i.e. acyl compounds of (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol;
4) by step 2) or step 3) gained (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acyl group
Compound is added in the oxolane prepared by a certain percentage and the mixed solution of Lithium hydrate, and be stirred overnight at room temperature reaction,
Detection detection extent of reaction, reaction terminate after, cross column purification can obtain sterling (1r, 5s) -2- methyl -5- (1- methyl ethylene) -
2- cyclohexene -1- alcohol, the optical purity of final products can reach more than 99%;
Step 2) and step 3) described in acry radical donor be parachlorophenol acetass, its addition rubs for starting compound
1.0 ~ 1.5 times of that amount;Step 2) and step 3) described in Digestive Enzyme be porcine pancreatic lipase, its addition be raw material chemical combination
The 1% ~ 10% of amount of substance number;Racemization catalyst described in step 3) is acidic resins d006, and its addition is raw material chemical combination
The 5% ~ 20% of amount of substance;
The present invention with d- carvone for raw material hydrogenated reduce (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -
1- alcohol;Alcohol obtains (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acyl group through Dynamic Kinetic Resolution again
Compound, more final (1r, 5s) -2- methyl -5- (1- the methyl ethylene) -2- cyclohexene -1- alcohol that is hydrolyzed;Or through dynamic
Mechanics respectively obtain (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acyl compounds and
(1s, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol, separates (1r, the 5s) -2- methyl -5- (1- obtaining
Methyl ethylene) -2- cyclohexene -1- alcohol acyl compounds are again through hydrolysis operation, you can (1r, 5s) -2- methyl -5- (1- first
Base vinyl) -2- cyclohexene -1- alcohol.The features such as this method possesses simple to operate, product yield is high, optical purity is good, fragrant in d-
There is in the preparation research of celery ketone derivatives great guidance and using value.
Specific embodiment
Embodiment 1
1), under the conditions of 0 DEG C, add 250ml absolute methanol, 15gd- carvone in single-necked flask, after stirring 15min, add
13g sodium borohydride, after the completion of feeding intake, uses balloon sealed flask, keeps 0 DEG C of conditioned response 3.5h, tlc detects d- Apium graveolenss reactive ketone
Completely, stopped reaction;Go out sodium borohydride to no longer there being bubble to emerge with dilute hydrochloric acid solution, after methanol is evaporated off, uses 100ml dichloro
Methane extracts three times, combined dichloromethane, drying, can obtain (5s) -2- methyl -5- (1- methyl ethylene) -2- hexamethylene after concentration
Alkene -1- alcohol 14.67g, yield is 97.8%.
2) in constant-temperature table, with 200ml indigo plant lid bottle as reaction vessel, 60ml toluene, (5s) -2- first of 7.5g are added
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol, 11g parachlorophenol acetass, 0.6g porcine pancreatic lipase ppl, 1.5g acid
Property resin d006, feeding intake finishes, and is warming up to 40 DEG C and is reacted, after 12 hours, detect (5s) -2- methyl -5- (1- methyl second
Thiazolinyl) disappearance of -2- cyclohexene -1- alcohol, it is converted into (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol second
Acyl compound;Reacted solution is cooled down, filter, concentrate, obtain crude product.
3) by step 2) in gained crude product be added in 150ml oxolane, and add Lithium hydrate 7g, be stirred at room temperature
Carry out reacting 24 hours, point plate detection (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetyl chemical combination
Stopped reaction when object point disappears;After adding 150ml water, reactant liquor is concentrated, is boiled off oxolane, then with dichloromethane pair
Surplus solution carries out extracting, divides liquid, drying, is concentrated to give containing (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- hexamethylene
The crude product of alkene -1- alcohol.
4) step 3) gained is contained the crude product of (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol
The petroleum ether being 10:1 with volume ratio carries out silica gel column chromatography with the mixed solution of ethyl acetate.(1r, 5s) -2- first finally can be obtained
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol 7.02g, yield 93.6%, after testing, final products (1r, 5s) -2- first
The ee value of base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol is 99.6%.
5) in constant-temperature table, with 200ml indigo plant lid bottle as reaction vessel, 90ml toluene, (5s) -2- first of 15.2g are added
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol, 20g parachlorophenol acetass, 1.1g porcine pancreatic lipase ppl, have fed intake
Finish, be warming up to 45 DEG C and reacted, after 6 hours, detect (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol
Conversion ratio reaches 50%;Stopped reaction, reacted solution is cooled down, filter, concentrates, crosses post, respectively obtain (1s, 5s) -2- first
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol 7.50g, s configuration yield is 98.7%, product ee value 99.9%;(1r,
5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetyl compounds 9.48g, yield is 97.7%.
6) will be acetylating for gained in step 5) (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol
Compound 9.48g is added in 150ml oxolane, and adds Lithium hydrate 7g, is stirred at room temperature and carries out reacting 24 hours, point plate inspection
Survey stopped reaction when (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetyl compound point disappears;Plus
After entering 150ml water, reactant liquor is concentrated, boiled off oxolane, then with dichloromethane, surplus solution carried out extracting, divide
Liquid, drying, concentration, excessively column purification, obtain (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol 7.01g,
This walks yield 97.3%, and product ee value is 99.6%.
Embodiment 2
1), under the conditions of 0 DEG C, add 1000ml absolute methanol, 150gd- carvone in single-necked flask, after stirring 20min, add
150g sodium borohydride, after the completion of feeding intake, uses balloon sealed flask, keeps 0 DEG C of conditioned response 4h, tlc detects d- Apium graveolenss reactive ketone
Completely, stopped reaction;Dilute hydrochloric acid solution goes out sodium borohydride to no longer there being bubble to emerge, and uses 400ml acetic acid after methanol is evaporated off
Ethyl ester extracts three times, combined ethyl acetate, drying, can obtain (5s) -2- methyl -5- (1- methyl ethylene) -2- hexamethylene after concentration
Alkene -1- alcohol 149.42g, yield is 98.3%.
2) in constant-temperature table, with 1000ml indigo plant lid bottle as reaction vessel, 700ml toluene, (5s) -2- first of 76g are added
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol, 110g parachlorophenol acetass, 7g porcine pancreatic lipase ppl, 15g are acid
Resin d006, feeds intake and finishes, and is warming up to 40 DEG C and is reacted, and after 12 hours, detects (5s) -2- methyl -5- (1- ethylene methacrylic
Base) disappearance of -2- cyclohexene -1- alcohol, it is converted into (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetyl
Compound;Reacted solution is cooled down, filter, concentrate, obtain crude product.
3) by step 2) in gained crude product be added in 600ml oxolane, and add Lithium hydrate 80g, room temperature is stirred
Mix and carry out reacting 24 hours, point plate detection (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetylation
Stopped reaction when compound point disappears;After adding 300ml water, reactant liquor is concentrated, is boiled off oxolane, then used dichloromethane
Surplus solution is carried out extract, divide liquid, drying, be concentrated to give containing (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- hexamethylene
The crude product of alkene -1- alcohol.
4) step 3) gained is contained the crude product of (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol
The petroleum ether being 10:1 with volume ratio carries out silica gel column chromatography with the mixed solution of ethyl acetate.(1r, 5s) -2- first finally can be obtained
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol 71.21g, yield 93.7%, after testing, final products (1r, 5s) -2- first
The ee value of base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol is 99.3%.
5) in constant-temperature table, with 1000ml indigo plant lid bottle as reaction vessel, 700ml toluene, (5s) -2- first of 76g are added
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol, 110g parachlorophenol acetass, 7g porcine pancreatic lipase ppl, have fed intake
Finish, be warming up to 45 DEG C and reacted, after 6 hours, detect (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol
Conversion ratio reaches 50%;Stopped reaction, reacted solution is cooled down, filter, concentrates, crosses post, respectively obtain (1s, 5s) -2- first
Base -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol 37.39g, s configuration yield is 98.4%, product ee value 99.9%;(1r,
5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetyl compounds 47.92g, r configuration yield is 98.8%.
6) by gained in step 5) (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol second elder generation base
Compound 47.92g is added in 600ml oxolane, and adds Lithium hydrate 70g, is stirred at room temperature and carries out reacting 24 hours, puts plate
Stopped reaction when detection (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acetyl compound point disappears;
After adding 300ml water, reactant liquor is concentrated, is boiled off oxolane, then with dichloromethane, surplus solution carried out extracting, divide
Liquid, drying, concentration, excessively column purification, obtain (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol 36.57g,
This walks yield 97.4%, and product ee value is 99.6%.
Claims (4)
1. a kind of alcoholization of d- carvone and Chiral Separation method are it is characterised in that it is to be realized by following operating procedure
:
1) under condition of ice bath, with alcohol as solvent, add raw material d- carvone, sodium borohydride by a certain percentage, then keep low temperature
Under the conditions of reacted, obtain compound, i.e. (5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol;
2) in organic solvent toluene, with step 1) gained compound as raw material, by a certain percentage add acry radical donor, fat
Enzyme, carries out kinetic resolution reaction at a certain temperature, obtains compound, i.e. (1r, 5s) -2- methyl -5- (1- ethylene methacrylic
Base) -2- cyclohexene -1- alcohol acyl compounds;And compound, that is, (1s, 5s) -2- methyl -5- (1- methyl ethylene) -
2- cyclohexene -1- alcohol;After reaction terminates, filter, concentrate, crossing column purification respectively to pure compound and compound;
3) in organic solvent toluene, with step 1) gained compound, add acry radical donor, Digestive Enzyme by a certain percentage, disappear
Rotation catalyst carries out Dynamic Kinetic Resolution reaction at a certain temperature, compound can be fully converted to compound,
The i.e. acyl compounds of (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol;
4) by step 2) or step 3) gained (1r, 5s) -2- methyl -5- (1- methyl ethylene) -2- cyclohexene -1- alcohol acyl group
Compound is added in the oxolane prepared by a certain percentage and the mixed solution of Lithium hydrate, and be stirred overnight at room temperature reaction,
Detection detection extent of reaction, reaction terminate after, cross column purification can obtain sterling (1r, 5s) -2- methyl -5- (1- methyl ethylene) -
2- cyclohexene -1- alcohol, the optical purity of final products can reach more than 99%, and product yield is preferable;According to above step
Described, equation of the present invention is as follows:
2. according to claim 1 a kind of alcoholization of d- carvone and Chiral Separation method it is characterised in that: step 2)
And step 3) described in acry radical donor be parachlorophenol acetass, its addition be starting compound mole 1.0
~1.5 times.
3. according to claim 1 a kind of alcoholization of d- carvone and Chiral Separation method it is characterised in that: step 2)
And step 3) described in Digestive Enzyme be porcine pancreatic lipase, its addition be starting compound mass number 1%~10%.
4. according to claim 1 a kind of alcoholization of d- carvone and Chiral Separation method it is characterised in that: step 3)
Described in racemization catalyst be acidic resins d006, its addition be starting compound quality 5%~20%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610801075.9A CN106365956A (en) | 2016-09-04 | 2016-09-04 | Method of alcoholization of D-carvone and separation of enantiomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610801075.9A CN106365956A (en) | 2016-09-04 | 2016-09-04 | Method of alcoholization of D-carvone and separation of enantiomer |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106365956A true CN106365956A (en) | 2017-02-01 |
Family
ID=57900529
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610801075.9A Pending CN106365956A (en) | 2016-09-04 | 2016-09-04 | Method of alcoholization of D-carvone and separation of enantiomer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106365956A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1137264A (en) * | 1994-10-19 | 1996-12-04 | 弗门尼舍有限公司 | Method for preparing alcohols |
CN102127584A (en) * | 2010-12-27 | 2011-07-20 | 浙江大学 | Dynamic kinetic method for resolving secondary alcohol |
CN102154431A (en) * | 2010-12-27 | 2011-08-17 | 浙江大学 | Kinetic resolution method of secondary alcohol |
CN104262093A (en) * | 2014-10-09 | 2015-01-07 | 王同俊 | R-1-(3-methylphenyl)ethanol and synthesis of ester thereof |
-
2016
- 2016-09-04 CN CN201610801075.9A patent/CN106365956A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1137264A (en) * | 1994-10-19 | 1996-12-04 | 弗门尼舍有限公司 | Method for preparing alcohols |
CN102127584A (en) * | 2010-12-27 | 2011-07-20 | 浙江大学 | Dynamic kinetic method for resolving secondary alcohol |
CN102154431A (en) * | 2010-12-27 | 2011-08-17 | 浙江大学 | Kinetic resolution method of secondary alcohol |
CN104262093A (en) * | 2014-10-09 | 2015-01-07 | 王同俊 | R-1-(3-methylphenyl)ethanol and synthesis of ester thereof |
Non-Patent Citations (1)
Title |
---|
MONICA NARDI等: "Eco-friendly stereoselective reduction of a,b-unsaturated carbonyl compounds by Er(OTf)3/NaBH4 in 2-MeTHF", 《TETRAHEDRON》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Sib et al. | Stereoselective total synthesis of bisorbicillinoid natural products by enzymatic oxidative dearomatization/dimerization | |
BR112015023334B1 (en) | process for producing (r)-3-hydroxybutyl (r)-3-hydroxybutyrate | |
EP2348008A1 (en) | Methods for the synthesis of acrylic acid and derivatives from fumaric acid | |
CN104151169B (en) | The method of optical voidness S-1-phenethylamine is prepared in a kind of fractionation | |
CN104263796B (en) | A kind of preparation method of the tetrahydro naphthylamines of R 1 | |
CN103497978B (en) | A kind of preparation method of high optical voidness L carnitines | |
CN107746834A (en) | For preparing the method and intermediate of Pregabalin | |
CN104151171B (en) | The method of optical voidness R-1-naphthalene ethylamine is prepared in a kind of fractionation | |
CN104276956A (en) | Method for preparing S-1-tetralin amine | |
CN103193636B (en) | A kind of method of synthesizing 2,3-butanediol ester | |
CN106365956A (en) | Method of alcoholization of D-carvone and separation of enantiomer | |
CN103193596B (en) | Method for synthetizing 2,3-butanediol | |
CN104726513B (en) | A kind of method that enzyme process prepares levodopa | |
CN101845476A (en) | Method for preparing L-tertiary leucine compound by two enzyme system | |
CN101709033A (en) | Method for preparing methyl ester levulinate by alcoholysis of hexamylose in near-critical methanol | |
CN103724217B (en) | A kind of method of asymmetric synthesis of D-Tyrosine | |
CN103214543B (en) | New Crategolic acid derivative, its preparation method and the application in antitumor drug thereof | |
CN106467454A (en) | Germacrone reduction and fractionation | |
CN104327034B (en) | 5 and 7 ester group catechin molecule method for selective production | |
CN106905162B (en) | A kind of preparation method of 3- benzyloxymethyl -4- aromatic radical -5- nitro -1- formyl cyclohexene | |
CN106349013A (en) | +-Nootkatone derivative | |
CN105316369A (en) | Process for enzymatic synthesis of (R)-4-cyano-3-hydroxybutyrate from sodium alginate immobilized halogenohydrin dehalogenase | |
CN106282293A (en) | The reduction of tonalid and fractionation | |
CN106119307B (en) | Preparation method of alpha-ketoglutaric acid | |
CN106380373A (en) | Germacrone alcoholization and biological resolution method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170201 |
|
WD01 | Invention patent application deemed withdrawn after publication |