Alternative Palladium‐Catalyzed Vinylic C−H Difluoroalkylation of Ketene Dithioacetals Using Bromodifluoroacetate Derivatives.

Abstract: A palladium‐catalyzed cross‐coupling of α‐oxo ketene dithioacetals and bromodifluoroacetate derivatives has been developed for the synthesis of a class of CF2‐containing tetra‐substituted olefins, which has potential to extend to drug design and material application. The process is proposed to involve two single electron transfer processes accompanied by an alternative loop from palladium(0) to palladium(I), likely due to unique structural properties of ketene dithioacetals with β,β‐dialkylthiol substituents on the olefin double bond. [ABSTRACT FROM AUTHOR]