From cycloolefins to chiral, polyfunctionalized linear C6/C12 building blocks—biocatalysis, (−)-conduramine E

1,4-Cyclohexadiene is the starting material for the expeditious synthesis of the 1S2S3S4R- and 1R2R3R4S-epoxy-cyclohexene-1,4-diol monoacetates through enzyme-catalyzed hydrolysis and transesterification, respectively. The absolute configurations are established by correlation of (−)-10 and known (+)-conduramine E. Ozonation and functional group manipulation open access to fully protected, polyfunctionalized C6-aldehydes whose reductive coupling to C2-symmetrical C12 building blocks is being explored.