Gold-catalyzed electrophilic activation of 1,1-difluoroallenes: α- and γ-selective addition of heteroatom nucleophiles

Abstract

Transition metal-catalyzed nucleophilic addition of heteroatom nucleophiles to 1,1-difluoroallenes has been demonstrated here for the first time. Treatment of 1,1-difluoroallenes with O-nucleophiles, such as phenols, carboxylic acids, and sulfonic acids, facilitated unprecedented α-selective addition in the presence of AuCl3 or AuCl(PPh3)/AgSbF6 catalysts which afforded 1,1-difluoroallyl alcohol derivatives. In contrast, amides and thiols underwent γ-selective addition to 1,1-difluoroallenes on their nitrogen or sulfur centers to provide 3,3-difluoroallyl amine and thiol derivatives.