Controlling the Facial Selectivity of Asymmetric [4 + 2] Cyclo-additions: A Concise Synthesis of the <i>cis</i>-Decalin Core Structure of Superstolides A and B

Abstract

Regio-, stereo-, and facial selective [4 + 2] cycloadditions between highly activated vinyl sulfones and 1,3-dienes derived from (R)-4-tert-butyldimethylsilyloxy-2-cyclohexen-1-one provide a powerful approach for the asymmetric synthesis of compounds containing the bicyclo[2.2.2]octanone carbon skeleton. This new methodology has been successfully applied to the asymmetric synthesis of the cis-decalin core structure of the potent anticancer marine natural products superstolides A and B.