Kinetic resolution of racemic alpha-arylalkanoic acids with achiral alcohols via the asymmetric esterification using carboxylic anhydrides and acyl-transfer catalysts.
A variety of optically active carboxylic esters are produced by the kinetic resolution of racemic alpha-substituted carboxylic acids using achiral alcohols, aromatic or aliphatic carboxylic anhydrides, and chiral acyl-transfer catalysts. The combination of 4-methoxybenzoic anhydride (PMBA) or pivalic anhydride with the modified benzotetramisole-type catalyst ((S)-beta-Np-BTM) is the most effective for promotion of the enantioselective coupling reaction between racemic carboxylic acids and a novel nucleophile, bis(alpha-naphthyl)methanol, to give the corresponding esters with high ee's. This protocol was successfully applied to the production of nonracemic nonsteroidal anti-inflammatory drugs from racemic compounds utilizing the transacylation process to generate the mixed anhydrides from the acid components with the suitable carboxylic anhydrides.
Shiina
Isamu
I
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. shiina@rs.kagu.tus.ac.jp
Nakata
Kenya
K
Ono
Keisuke
K
Onda
Yu-suke
YS
Itagaki
Makoto
M
D000438:Alcohols / Q000737:chemistry*; D000812:Anhydrides / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D013237:Stereoisomerism; D013773:Tetramisole / Q000031:analogs & derivatives* / Q000737:chemistry
D000438:Alcohols; D000812:Anhydrides; D002264:Carboxylic Acids; D004952:Esters; C515434:benzotetramisole; D013773:Tetramisole