Enantiopure vicinally trisubstituted all-cis-bis(hydroxymethyl)-cyclopentenols and their derivatives

Oxidations of {(1R,4R,5S)-2-[tert-butyl(dimethyl)silyloxy-methyl]-4-(trimethylsilyl)cyclopent-2-en-1-yl}methanol with m-chloroperoxybenzoic acid (mCPBA) and dimethyldioxirane were studied. In the case of mCPBA, an allylicic alcohol expected according to the protodesilylation mechanism and an anomalous product of 1,2-migration of the Me₃Si group were obtained. The latter was formed due to the coordination and directing effects of the free OH group.