Direct Deoxygenation of α-Hydroxy and α,β-Dihydroxy Ketones Using a Silyl Lithium Reagent.

A reliable method for the one-step direct deoxygenation of α-hydroxy ketones has been developed using a silyl lithium reagent and acetic anhydride. The method is metal-catalyst-free and does not require prefunctionalization of the hydroxy group prior to its removal. Deoxygenation of different primary, secondary, and tertiary alcohols was carried out with up to 98% isolated yield.

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

A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and -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.