GB1592536A - Process for producing optically active a-hydroxycarboxylic acid ester - Google Patents
Process for producing optically active a-hydroxycarboxylic acid ester Download PDFInfo
- Publication number
- GB1592536A GB1592536A GB771178A GB771178A GB1592536A GB 1592536 A GB1592536 A GB 1592536A GB 771178 A GB771178 A GB 771178A GB 771178 A GB771178 A GB 771178A GB 1592536 A GB1592536 A GB 1592536A
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- Prior art keywords
- acid ester
- optically active
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process is created for preparing optically active alpha -hydroxycarboxylic esters, in which an alpha -ketocarboxylic ester is asymmetrically hydrogenated, namely in the presence of a rhodium complex with a phosphine ligand having an optically active substituent group which is derived from natural sources.
Description
(54) PROCESS FOR PRODUCING OPTICALLY ACTIVE
a-HYDROXYCARBOXYLIC ACID ESTER
(71) We, (ZAIDANHOJIN) SAGAMI CHEMICAL RESEARCH
CENTER, a Japanese Company of No. 4-5, Marunouchi l-chome, Chiyoda-ku,
Tokyo, Japan do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to a process for producing an optically active ahydroxycarboxylic acid ester.
The optically active a-hydroxycarboxylic acid esters to which this invention relates are physiologically active compounds which occur naturally and include lactic acid esters, mandelic acid esters and pantoyl lactones.
It is well known that optically active D-(-)-pantoyl lactone is an important intermediate for producing pantothenic acid, pantotheine and Coenzyme A.
Calcium pantothenate has been produced on an industrial scale as a member of a vitamin complex. Pantothenic acid is a component of Coenzyme A and has coenzymatic activity. Pantothenyl alcohol and pantothenyl ethyl ether, which are derivatives of pantothenic acid, have also been produced on an industrial scale.
Calcium pantothenate can be produced by reacting pantolactone with the calcium salt of p-alanine without a racemization (E. H. Wilson, J. Weijlard and M.
Tishler, J. Amer. Chem. Soc., 76 5177 (1954)). In this process it is important to ensure that D-(-)-pantoyl lactone is produced. In the cases of the production of pantotheine, pantothenyl alcohol and pantothenyl ethyl ether, the problem of correct optical configuration is also important.
The products of the present invention are important as intermediates for the synthesis of amino acids and derivatives thereof.
Heretofore, it has been known to produce the optically active ahydroxycarboxylic acid ester from a-ketocarboxylic acid ester by hydrogenation in the presence of a catalyst, for which two methods are as follows:
1) Hydrogenation of an optically active a-ketocarboxylic acid ester in the presence of a catalyst (A. McKenzie, J. Chem. Soc., 87, 1373 (1905); Mitsui and
Kanai J. Japanese Chem. Soc., 87, 179 (1966)).
2) Asymmetric hydrogenation in the presence of a rhodium complex having an optically active phosphine ligand containing a ferrocenyl group (Mise, Hayashi and
Kumada Chem. Soc. Japan, 35th Annual Meeting Abstract lK-20 (1976)).
However, in the conventional method 1), an optically active compound is itself required as the starting material in the asymmetric synthesis whereas in the present invention only a catalytic amount of the optically active compound is used to obtain the desired compound. Accordingly, the conventional method 1) is disadvantageous in principle.
In the conventional method 2) the optically active phosphine is a compound having complicated structure and metal component, which is not easily produced because the synthesis includes an optical resolution and the optical yield is low.
Heretofore, D-(-)-pantoyl lactone has been produced by an optical resolution of racemic pantonyl lactone with e.g. quinine and ephedrine.
In this method, the maximum theoretical yield which can be obtained is 50%.
Since L-(+)-pantonyl lactone has no physiological activity, it has to be converted to racemic pantonyl lactone by a difficult racemization process since otherwise it is wasted.
The present invention provides a process for producing an optically active ahydroxycarboxylic acid ester which comprises an asymmetric hydrogenation of an a-ketocarboxylic acid ester in the presence of a rhodium complex with a phosphine ligand which is (a) a dioxolan having optically active carbon atoms at at least the 4and 5-positions and which has the formula
wherein the asterisk (*) represents an optically active position; R' to R4 each represents an alkyl, aralkyl or aryl group; and R5 and R6 each represents a hydrogen atom or an alkyl, aryl, alkoxy, aminocarbonyl, carboxyl, carboxylic ester, cyano, alkylthio or arylthio group or R5 and R6 together complete a cycloalkylidene ring, or (b) a pyrrolidine having optically active positions at at least the 2- and 4-positions and which has the formula
wherein the asterisk (*) represents an optically active position; R1' to R4' each represents an alkyl or aryl group; R5' and R6' each represents a hydrogen atom or an alkyl or aryl group and R7' represents a hydrogen atom or an alkyl, aryl, carboxylic ester, amino, carboxyl or cyano group.
In this way it is possible to obtain an optically active a-hydroxycarboxylic acid ester having high optical purity in high yield in an industrial process.
Suitable a-ketocarboxylic acid esters used in the process of the present invention include pyruvic acid esters such as methyl pyruvate and n-propyl pyruvate; benzoylformic acid esters such as ethyl phenyl-glyoxylate and cyclohexyl phenylglyoxylate; alkyl a-ketocarboxylic acid esters such as methyl pentylglyoxylate and ethyl octylglyoxylate; cr-ketolactones such as a-keto-,6-dimethyl-y- butyrolactone.
The catalyst used in the process of the present invention is a rhodium complex with a phosphine ligand having an optically active substituent group. Suitable dioxolans having the formula (I) include (2R,3R)-2, 3-O-isopropylidene-2,3-di hydroxy- 1 ,4-bis(diphenylphosphino)butane and (2S,3S)-2,3-O-isopropylidene-2,3 dihydroxy- 1 ,4-bis(diphenylphosphino)butane; (2R,3R) or (2S,3S)-2,3-O-iso- propylidene-2,3-dihydroxy- 1 ,4-bis(dibenzylphosphino)butane; (2R,3R) or (2S,3S) 2,3-O-isopropylidene-2,3-dihydroxy- 1 ,4-bis(di-o-tolylphosphino)butane; (2R,3R) or (2S,3S)-2,3-O-isopropylidene-2,3-dihydroxy- 1 ,4-bis(di-m-tolylphosphino) butane; (2R,3R) or (2S,3S)-2,3-O-isopropylidene-2,3-dihydroxy-l ,4-bis(di-2,5-xylyl- phosphino)butane; (2R,3R) or (2S,3S)-2,3-O-benzylidene-2,3-dihydroxy-l ,4-bis(di- phenylphosphino)butane; (2R,3R) or (2S,3S)-2,3-O-cyclohexylidene-2,3-di hydroxy- I ,4-bis(diphenylphosphino)hutane; (2R,3R) or (2S,3S)-2,3-O-cyclo- pentylidene-2,3-dihydroxy-l ,4-bis(diphenylphosphino)butane and (2R,3R) or (2S,3S) - 2,3 - O - cyclohexylidene - 2,3 - dihydroxy - 1,4 - bis(cyclohexylphenyl phosphino)butane.
Suitable pyrrolidines having the formula (II) include (2S,4S)-N-t-butoxy carbonyl-4-diphenylphosphino-2-diphenylphosphinomethyl pyrrolidine and (2S,4S)4-diphenylphosphino-2-diphenylphosphinomethyl pyrrolidine.
In the process of the present invention, it is preferable to use a solvent.
Suitable solvents include aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol and ethanol and ethers such as tetrahydrofuran, monoglyme; and mixtures thereof
In the process of the present invention, the a-ketocarboxylic acid ester starting material is preferably dissolved in a solvent and the rhodium complex catalyst is added at a catalytic amount of 0.01 to 1.0 mole 0% and the reaction is carried out in hydrogen at a pressure of 1 to 50 atmospheres. The reaction is smoothly performed at room temperature without using the special heating or cooling means and the object product can be obtained at substantially stoichiometric yield.
In order to reduce the reaction time, it is preferable to perform the reaction
under higher pressure such as several to several tens atms, and at higher temperatures.
The present invention will be further illustrated by the following examples.
Example 1.
Under an argon atmosphere, 38 mg of [Rh(1,5-cyclooctadiene)CI]2 and 100 mg
of (2S,4S)-N-butoxycarbonyl-4-diphenylphosphino-2-diphenylphosphinomethyl pyrrolidine (hereinafter referred to as BPPM) were dissolved in 8 ml of tetrahydrofuran to prepare a solution of the catalyst.
In an autoclave, the solution of the catalyst and 3.90 g of n-propyl pyruvate were charged and the reaction was carried out under hydrogen at 20 atm. at 200C for 24 hours with stirring to complete the reaction. The solvent was distilled off
from the reaction mixture and the product was distilled to obtain 3.76 g of n-propyl
(+)-lactate having a boiling point of 620C/l 1 mmHg, I3]D8 + 9.17 (neat) and an
optical purity of 76% (yield: 95%).
Examples 2 to 15.
In accordance with the process of Example 1 but using various a- ketocarboxylic acid esters, optically active ligands and solvents, the optically active
a-hydroxycarboxylic acid esters were produced. The results are shown in Table 1.
In Table 1, the optically active ligand (-)-DIOP means (2R,3R)-2,3-O-iso- propylidene-2,3-dihydroxy- 1 ,4-bis(diphenylphosphino)butane and (+ )-DlOP means (2S,3S)-2,3-O-isopropylidene-2,3-dihydroxy- 1 ,4-bis(diphenylphosphino)- butane.
Example 16.
In accordance with the process of Example 1, 19 mg of [Rh(l,5
cyclooctadiene) Cl]2 and 50 mg of an optically active ligand of BPPM were dissolved in 4 ml of tetrahydrofuran to prepare a solution of the catalyst.
In an autoclave, the solution of the catalyst and 1.92 g of a-keto-p,p-dimethyl- y-butyrolactone were charged and the reaction was carried out under hydrogen of
50 atm. at 200C for 24 hours with stirring to complete the reaction. The solvent was distilled off from the reaction mixture and the product was purified by passing through a short silica gel chromatography column using n-hexane-ether as elute to obtain 1.89 g of(-)-pantoyl lactone having a melting point of 89 to 910C and [a]025- 25.3 (C. 2.00; H2O) and an optical activity of 50% (yield: 97%).
Examples 17 and 18.
In accordance with the process of Example 16 except using various optically active ligands and solvents, the optically active (-)-pantoyl lactone was produced.
The results are also shown in Table 1.
TABLE 1
Optically 8 vb o o active zeal os o cre s acid ester ligand Solvent Product D purity s ec) Yield () 2 CH3COCOOCH3 BPPM to CH3CHCOOCH *5M n oo 100 "n 1K c 1 e * a OH oo t O t n O cs O t. CH3COCOOCll3 BPPM MeOH CH3CHCOOCH3 o tA + + + + 95 OH 5 CH3COCOOCH3 (-)-DIOP PhH 30 317 100 u u u u u u u O o o o o o o 1 0 0 0 0 0 0 0 6 CH3COCOOCH3 +U--o +u--o THF CH3CHCOOCH3 +u--O 412 99 u u u u u u u * 7 CH3COCOOCH3 (-)DIOP Monoglyme CH3CHCOOCH3 +3t2 378 99 OH 8 CH3COCOOCH3 (-)-DIOP MeOH +150 o 95 a a a a K W C s oV > oV a V s V z g C ) V G t s s s s O O O *,-~ V V V V V V V U U U b U U V U ca C q < , t m xo > Oo TABLE 1 (cont.)
Optically a-Ketocarboxylic active 1820 Optical E: acid ester ligand Solvent Product purity(%ee) Yield 8 8 9 CH3COCOOnPr BPPM PhH CH3CHCOOnPr +9,17 75.8 99 OH s oowo CH3COCOOPr (-)-DIOP ThF CH3CHCOOPr +5.07 41.9 100 OH 11 CH3COCOOiBu BPPM om CH3CHCOO1Bu +10.70 cs5-5a; OH * 12 CH3COCOOBu BPPM ThF CH3CHCOO1Bu +10,76 71.1 100 OH * a CH3COCOOiBu (-)-DIOP ThF CH3CHCOOiBu +5,73 d 8 99 OH * * =-ox * H-o * =- * u-o * v-o * =-ox * U--0 zv PhCOCOOEt (+)-DIOP THF PhCHCOOEt (CHCl3, = v v 98 C204) OH a CZ (+)-DIOP THF PhCHCOO (EtOH, 2.8 93 C2.13) a a a a c h > = 2 o E 2 H ~ 0we X l X X l l l z X ~ m . m vl +.
~ o o ms m m ;i 9 oY t v 8 v v v 8 8 or 8 8 8 8 8 Ov Ov : = x :c a: t v v . V V V G E aE o ~ n e m TABLE 1 (cont.)
Optically s Example acid ester ligand Solvent Product D purityo Yield (%) e no o o (H2O, 18 009 tlzn < r O O c g ~ CL mg D ~ 4 e Note: BPPM, (-)-DIOP, (+)-DIOP are defined above.
PhH: benzene
THF: tetrahydrofuran
MeOH: methanol
Monoglyme: 1,2-dimethoxyethane Example 19.
In accordance with the process of Example 16, 24.2 mg of [Rh(1,5cyclooctadiene) Cl]2 and 60.2 mg of BPPM were dissolved in 8 ml of benzene to prepare the solution of the catalyst. In an autoclave, the solution of the catalyst and 1.28 g of α-keto- , -dimethyl-γ-butyrolactone were charged and the reaction was carried out under initial hydrogen pressure of 50 atm at 30 C for 48 hours with stirring in a thermostat-temperature-controlled bath. The reaction was completed at a conversion of 100%. The solvent and the catalyst were separeted as the process of Example 16 to obtain 1.28 g of (-)-pantoyl lactone having [α]D25 - 42.5 (C.
2.046-H2O) and an optical purity of 83.9% (yield: 98.4%).
Example 20.
In accordance with the process of Example 19 except varying the reaction temperature to 400C and the initial hydrogen pressure to 20 atm the reaction was carried out and the reaction mixture was distilled under a reduced pressure without separating the catalyst to obtain 1.20 g of (-) pantoyl lactone having a boiling point of 92 C/4 mmHg a melting point of 89 to 91 C, [α]D25 - 43.3 (C. 2.033:H2O) and an optical purity of 85.4% (yield:92.3%).
Example 21.
In accordance with the process of Example 19 except varying the reaction temperature to 500 C, the reaction and the separation were carried out to obtain 1.23 g of (-) pantoyl lactone having ICE]D5 - 43.00 (C. 2.042:H20) and an optical purity of 84.8% (yield: 94.6%).
Example 22.
In accordance with the process of Example 20 except varying the reaction temperature to 700 C, the reaction and the separation were carried out to obtain 1.18 g of (-) pantoyl lactone having [α]D25 - 39.1 (C. 2.128:H20) and an optical purity of 77.1% (yield: 90.7%).
Example 23.
In accordance with the process of Example 21 except using 8 ml of toluene as the solvent, the reaction and the separation were carried out to obtain 1.25 g of (-) pantoyl lactone having [aS]25 - 39.4 (C. 2.032:H20) and an optical purity of 77.7% (yield: 96.2%).
Claims (10)
1. A process for producing an optically active a-hydroxycarboxylic acid ester which comprises an asymmetric hydrogenation of an a-ketocarboxylic acid ester in the presence of a rhodium complex with a phosphine ligand which is (a) a dioxolan having optically active carbon atoms at at least the 4- and 5-positions and which has the formula
wherein the asterisk (*) represents an optically active position; R' to R4 each represents an alkyl, aralkyl or aryl group; and R5 and R6 each represents a hydrogen atom or an alkyl, aryl, alkoxy, aminocarbonyl, carboxyl, carboxylic ester, cyano, alkylthio or arylthio group or R5 and R6 together complete a cycloalkylidene ring, or (b) a pyrrolidine having optically active positions at at least the 2- and 4-positions and which has the formula
wherein the asterisk (*) represents an optically active position; R' to R4' each represents an alkyl or aryl group; R5' and R5' each represents a hydrogen atom or an alkyl or aryl group and R7' represents a hydrogen atom or an alkyl, aryl, carboxylic ester, amino, carboxyl or cyano group.
2. A process according to claim 1 wherein the reaction is carried out under hydrogen at a pressure of 1 to 50 atm.
3. A process according to claim I or claim 2 wherein the reaction is carried out by dissolving the a-ketocarboxylic acid ester in a solvent.
4. A process according to claim 3 wherein the solvent is an aromatic hydrocarbon, an alcohol, an ether or a mixture thereof.
5. A process according to any preceding claim wherein the a-ketocarboxylic acid ester is a pyruvic acid ester, a benzoylformic acid ester, an alkylglyoxylic acid ester or an a-ketolactone.
6. A process according to claim 5 wherein the a-ketocarboxylic acid ester is a pyruvic acid ester and the product is an optically active lactic acid ester.
7. A process according to claim 5 wherein the a-ketocarboxylic acid ester is a keto-p,/3-dimethyl-y-butyrolactone and the product is an optically active pantoyl lactone.
8. A process according to any preceding claim wherein the catalyst is added in an amount of 0.01 to 1.0 mole %.
9. A process according to claim I substantially as herein described with reference to the Examples.
10. An a-hydroxy-carboxylic acid ester made by a process according to any preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2029377A JPS53105421A (en) | 1977-02-28 | 1977-02-28 | Preparation of optical active alpha-hydroxycarboxylic acid esters acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1592536A true GB1592536A (en) | 1981-07-08 |
Family
ID=12023106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB771178A Expired GB1592536A (en) | 1977-02-28 | 1978-02-27 | Process for producing optically active a-hydroxycarboxylic acid ester |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS53105421A (en) |
| CA (1) | CA1109479A (en) |
| CH (1) | CH635815A5 (en) |
| GB (1) | GB1592536A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2504534A1 (en) * | 1981-04-22 | 1982-10-29 | Hoffmann La Roche | PHOSPHINS, THEIR PREPARATION, RHODIUM COMPLEXES OF THESE PHOSPHINS AND THEIR USE AS CATALYSTS |
| FR2521145A1 (en) * | 1982-02-05 | 1983-08-12 | Hoffmann La Roche | CHIRAL PHOSPHINS, PROCESSES FOR THEIR PREPARATION, INTERMEDIATE PRODUCTS OF THEIR PREPARATION, RHODIUM COMPLEXES OF THESE PHOSPHINS AND USE THEREOF IN ASYMMETRIC HYDROGENATIONS |
| EP0621075A2 (en) * | 1993-04-19 | 1994-10-26 | Kuraray Co., Ltd. | Novel rhodium-containing catalyst |
| EP2141145A1 (en) * | 2008-06-30 | 2010-01-06 | Uhde GmbH | Efficient and highly enantioselective Rh-catalyzed hydrogenations of unsaturated lactate precursors with chiral bisphospholanes as ligands |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5508435A (en) * | 1992-07-29 | 1996-04-16 | Merck & Co., Inc. | Asymmetric hydrogenation of beta- or gamma-ketoesters and beta- or gamma-ketoamides |
-
1977
- 1977-02-28 JP JP2029377A patent/JPS53105421A/en active Granted
-
1978
- 1978-02-27 GB GB771178A patent/GB1592536A/en not_active Expired
- 1978-02-27 CA CA297,758A patent/CA1109479A/en not_active Expired
- 1978-02-27 CH CH209078A patent/CH635815A5/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2504534A1 (en) * | 1981-04-22 | 1982-10-29 | Hoffmann La Roche | PHOSPHINS, THEIR PREPARATION, RHODIUM COMPLEXES OF THESE PHOSPHINS AND THEIR USE AS CATALYSTS |
| FR2521145A1 (en) * | 1982-02-05 | 1983-08-12 | Hoffmann La Roche | CHIRAL PHOSPHINS, PROCESSES FOR THEIR PREPARATION, INTERMEDIATE PRODUCTS OF THEIR PREPARATION, RHODIUM COMPLEXES OF THESE PHOSPHINS AND USE THEREOF IN ASYMMETRIC HYDROGENATIONS |
| US4539411A (en) * | 1982-02-05 | 1985-09-03 | Hoffmann-La Roche Inc. | Rhodium complexes of chiral phosphines |
| US4620013A (en) * | 1982-02-05 | 1986-10-28 | Hoffmann-La Roche Inc. | Chiral phosphines |
| EP0621075A2 (en) * | 1993-04-19 | 1994-10-26 | Kuraray Co., Ltd. | Novel rhodium-containing catalyst |
| EP0621075A3 (en) * | 1993-04-19 | 1994-11-09 | Kuraray Co | Novel rhodium-containing catalyst. |
| US5434311A (en) * | 1993-04-19 | 1995-07-18 | Kuraray Co., Ltd. | Rhodium-containing catalyst |
| EP2141145A1 (en) * | 2008-06-30 | 2010-01-06 | Uhde GmbH | Efficient and highly enantioselective Rh-catalyzed hydrogenations of unsaturated lactate precursors with chiral bisphospholanes as ligands |
| WO2010000354A1 (en) * | 2008-06-30 | 2010-01-07 | Uhde Gmbh | Efficient and highly enantioselective rh-catalyzed hydrogenations of unsaturated lactacte precursors with chiral bisphospholanes as ligands |
Also Published As
| Publication number | Publication date |
|---|---|
| CH635815A5 (en) | 1983-04-29 |
| JPS53105421A (en) | 1978-09-13 |
| CA1109479A (en) | 1981-09-22 |
| JPS5622859B2 (en) | 1981-05-27 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |