Gold-Catalyzed [2,3]-Sigmatropic Rearrangement: Reaction of Aryl Allyl Alcohols with Diazo Compounds

A gold-catalyzed [2,3]-sigmatropic rearrangement reaction has been developed. The intermolecular rearrangement occurs between in situ generated donor–acceptor gold–carbenes and cinnamyl alcohols via tandem oxonium ylide formation. The desired rearranged product has been accomplished selectively over more conventional O–H insertion, cyclopropanation, cycloaddition, and C–H functionalization products under mild, open-air conditions. The scope of the work has been illustrated by synthesizing a new class of substrates that can be used for constructing complex molecular targets.