Asymmetrization of all-cis-3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane and of the 4-methyl and 4-ethyl substituted homologues

Abstract Enantiomerically pure mono acylated derivatives of cis , cis -3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane 1 , all- cis -3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 2 and all- cis -3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane 3 were obtained upon lipase catalyzed asymmetrization. PPL-catalyzed 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 obtained with SAM II lipase. On the other hand, enantiotoposelective hydrolysis of their diacetates and especially dibutyrates gave useful results only for the 4-substituted substrates and produced the ( S )-monoesters.