Kinetic Resolution of Racemic α-Arylalkanoic Acids with Achiral Alcohols via the Asymmetric Esterification Using Carboxylic Anhydrides and Acyl-Transfer Catalysts

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• 作者：Isamu Shiina ; Kenya Nakata ; Keisuke Ono ; Yu-suke Onda ; Makoto Itagaki
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：August 25, 2010
• 年：2010
• 卷：132
• 期：33
• 页码：11629-11641
• 全文大小：824K
• 年卷期：v.132,no.33(August 25, 2010)
• ISSN：1520-5126

文摘

A variety of optically active carboxylic esters are produced by the kinetic resolution of racemic α-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)-β-Np-BTM) is the most effective for promotion of the enantioselective coupling reaction between racemic carboxylic acids and a novel nucleophile, bis(α-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.