Palladium‐Catalyzed Cross‐Coupling between Alkylidenecyclopropanes and Boronic Acids

Abstract The combination of a Pd(0) source and a phosphoramidite ligand promotes a formal allylic cross‐coupling between alkylidenecyclopropanes (ACPs) and boronic acids to yield synthetically appealing 1,1‐disubstituted alkenes. Remarkably, the reaction proceeds both under neutral and basic conditions, and works with both aryl‐ and alkenylboronic acids. DFT calculations suggest that the reaction entails a C−C activation/protonation mechanism instead of a hydropalladation pathway, which has been frequently proposed for other metal‐promoted hydrofunctionalizations of ACPs.