Asymmetric hydrogenation of aromatic-substituted olefins using organorhenium catalyst

• US 5,187,136 A
• Filed: 06/17/1991
• Issued: 02/16/1993
• Est. Priority Date: 06/17/1991
• Status: Expired due to Fees

• Current Assignee: Albemarle Corporation
• Original Assignee: Ethyl Corporation (Newmarket Corporation)
• Inventors: Kolich, Charles H., Manimaran, Thanikavelu, Klobucar, W. Dirk
• Primary Examiner(s): Killos, Paul J.
• Assistant Examiner(s): Conrad, Joseph
• Application Number:
  US07/716,013
• Time in Patent Office: 610 Days
• Field of Search: 562/493, 562/496, 556/21, 556/45, 502/162
• US Class Current: 502/162
• CPC Class Codes: B01J 2231/645 of C=C or C-C triple bonds
• CPC Class Codes: B01J 2531/0266 Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
• CPC Class Codes: B01J 2531/74 Rhenium
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/24 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
• CPC Class Codes: B01J 31/2452 with more than one complexing phosphine-P atom
• CPC Class Codes: B01J 31/28 of the platinum group metals, iron group metals or copper
• CPC Class Codes: C07C 51/36 by hydrogenation of carbon-to-carbon unsaturated bonds
• CPC Class Codes: C07F 13/005 Compounds without a metal-carbon linkage

Abstract

A process for the asymmetric reduction of carboxylic acids of the formula ##STR1## or the amine salts thereof, where R and R₁ are the same or different and are hydrogen, alkyl, cycloalkyl or haloalkyl and Ar is aryl or substituted aryl is disclosed.

Claims

1. A process for preparing optically active α

-aryl aliphatic carboxylic acids which comprises catalytically, asymmetrically hydrogenating a carboxylic acid of the formula ##STR4## or the amine salt thereof, where R and R₁ are the same or different and are hydrogen, alkyl, cycloalkyl, or haloalkyl; and

Ar is aryl or substituted aryl;

by utilizing a catalytically effective amount of a mixture of (i) a rhenium-containing compound selected from the group consisting of halide, a mixed halide-chelate complex and a chelate complex and (ii) a chiral phosphine compound.

2. The process according to claim 1 wherein said rhenium compound is a halide, a mixed halide-chelate complex or a chelate complex.

3. The process of claim 1 wherein R and R₁ are the same or different and are hydrogen or alkyl.

4. The process according to claim 3 wherein R and R₁ are hydrogen.

5. The process according to claim 1 wherein Ar is phenyl or naphthyl substituted with alkyl or alkoxy.

6. The process according to claim 5 wherein Ar is phenyl substituted with methyl, ethyl, n-propyl or isobutyl.

7. A process for preparing optically active α

-aryl aliphatic carboxylic acids which comprises catalytically, asymmetrically hydrogenating a carboxylic acid of the formula ##STR5## or the amine salt thereof, where R and R₁ are the same or different and are hydrogen, alkyl, cycloalkyl, or haloalkyl; and

Ar is aryl or substituted aryl;

by utilizing a mixture of (i) a rhenium compound selected from the group consisting of halide, a mixed halide-chelate complex and a chelate complex and (ii) an optically active ligand where the ligand is ##STR6## where R'"'"' is hydrogen, alkyl, haloalkyl, aryl or substituted aryl.

8. The process according to claim 7 wherein said rhenium compound is a halide, a mixed halide-chelate complex or a chelate complex.

9. The process of claim 7 wherein R and R₁ are the same or different and are hydrogen or alkyl.

10. The process according to claim 9 wherein R and R₁ are hydrogen.

11. The process according to claim 7 wherein Ar is phenyl or naphthyl substituted with alkyl or alkoxy.

12. The process according to claim 11 wherein Ar is phenyl substituted with methyl, ethyl, n-propyl or isobutyl.

13. An asymmetric hydrogenation catalyst composition comprising a mixture of BINAP and ReCl₅ and optionally an organic amine and hydrogen.

14. A process for preparing S-ibuprofen which comprises catalytically, asymmetrically hydrogenating 2-(4-isobutylphenyl)acrylic acid by utilizing a mixture of rhenium(V) chloride and an optically active BINAP where BINAP is ##STR7##