Gold-Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross-Coupling Reactivity with Gold

A sp3–sp2 CC cross‐coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetalation, CBr oxidative addition, and CC reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development of novel transformations involving redox‐active gold catalysts. Teaching Au new tricks: A novel manifold for reactivity in gold catalysis has been realized, allowing the cross‐coupling of arylboronic acids and allylic bromides without a sacrificial oxidant. A bimetallic catalyst is employed, providing allylbenzene products with unique scope and chemoselectivity. A mechanistic proposal is put forward based on stoichiometric experiments, including the isolation of an AuIII allyl complex.