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

A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and Z-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 E-guggulsterone and E-volkendousin was also claimed using a short sequence.

Automated summary

A reliable method for enone transposition using silyl group masking was developed. The method highlights enantio-switching, substituent shuffling, and Z-selectivity. It was successfully applied for the total synthesis of peribysin D and claimed for the formal synthesis of E-guggulsterone and E-volkendousin.