Asymmetrization of all-cis-3,5-dihydroxy1-(methoxycarbonyl)cyclohexane andof the 4-methyl and 4-ethyl substituted homologues

Enantiomerically pure mono acylated derivatives of cis,cis-3, 5-dihydroxy-1 -(methoxycarbonyl)cyclohexane 1, all-cis-3,5-dihydroxy-4-methyl-1-(methoxyc arbonyl)cyclohexane 2 and all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl) cyclohexane 3 were obtained upon lipase catalyzed asymmetrization. PPL-cata lyzed transesterification of 1 with vinyl acetate led in high yield to the (S)-monoacetate (+)-13. With substrates 2 and 3 this process was slower and gave the (R)-monoacetates (-)-14 and (-)-15; the best results were obtaine d with SAM II lipase. On the other hand, enantiotoposelective hydrolysis of their diacetates and especially dibutyrates gave useful results only for t he 4-substituted substrates and produced the (S)-monoesters. (C) 2000 Elsev ier Science Ltd. All rights reserved.