Tuning of α-Silyl Carbocation Reactivity into Enone Transposition: Application to the Synthesis of Peribysin D, <i>E</i>-Volkendousin, and <i>E</i>-Guggulsterone

Abstract

A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and <i>Z</i>-selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision. Formal synthesis of <i>E</i>-guggulsterone and <i>E</i>-volkendousin was also claimed using a short sequence.