Aldehyde Olefination with Arylboroxines Enabled by Binary Rhodium Catalysis

A rhodium-catalyzed olefination of aliphatic aldehydes with arylboroxines is described. The simple rhodium(I) complex [Rh(cod)OH]2 without any external ligands or additives is able to catalyze the reaction in air and neutral conditions, allowing the construction of aryl olefins in an efficient manner with a good functional group tolerance. The mechanistic investigation illustrates that the binary rhodium catalysis is the key for the transformation, which involves a Rh(I)-catalyzed 1,2-addition and a Rh(III)-catalyzed elimination.