79(P01) 植物培養細胞を生体触媒とするアセテート類の不斉加水分解(ポスター発表の部)

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Biochemical hydrolysis is a useful method for the preparation of chiral alcohols as synthons for organic synthesis. We have investigated the asymmetric hydrolyses of acetates by the cultured cells of Marchantia polymorpha, i.e., kinetic resolution of racemic acetates, eantioselective hydrolysis of symmetric diacetates, and asymmetric induction into prochiral center of enol acetates. In the hydrolysis of racemic sec-acetates, such as trans- and cis-2-methylcyclohexanyl acetates (1 and 2), with cultured cells of M. Polymorpha, the configulation at the carbon atom bearing the hydroxyl group of their corresponding alcohols obtained was mainly R in each case. The hydrolysis was highly enantioselective: the enantiomeric excesses of the alcohols were more than 80% in a 50% yield. meso-1,2-Diacetoxycyclohexane (9), was converted stereoselectively into (1S,2R)-1-monoacetate. On the other hand, in the case of trans-1,2-diacetoxycyclohexane (10) as a substrate, (1R,2R)-enantiomer was preferentially hydrolyzed to the corresponding alcohol. The cultured cells were found to hydrolyze enantioselectively the acetoxyl group at the stereogenetic center of (R)-configulation of the symmetric 1,2-diacetoxycyclohexanes. When enol acetates were chosen as the substrates, the resulting ketones were optically active. 1-Acetoxy-2-methylcyclohexene (14) was quantitatively converted into (S)-2-methylcyclohexanone in 99%e.e. This shows that an attack of proton to an enol intermediate, which was obtained by hydrolysis of the acetate, occured from one specified side of the double bond of the enol.
天然有機化合物討論会の論文
1997-07-20

79(P01) 植物培養細胞を生体触媒とするアセテート類の不斉加水分解(ポスター発表の部)

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