Aerobic C-C Bond Cleavage of Allylic Alcohols via Co-Catalyzed Hydrogen Atom Transfer.

A simple, efficient method has been developed for the CoIII-H-catalyzed aerobic C-C bond cleavage of tertiary allylic alcohols to access ketones. This novel approach presents excellent chemoselectivity, good functional group compatibility, and high yields. This reaction occurs through a HAT-initiated peroxide intermediate, and an adjacent glycol-type diradical fragmentation process is recommended.