Nickel‐Catalyzed Allylic C(sp2)–H Activation: Stereoselective Allyl Isomerization and Regiospecific Allyl Arylation of Allylarenes

Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp 2 )–H activation by in‐situ‐formed Ni 0 , which is inserted into the C–H bond at the 2‐position of the allyl moiety without a directing group. The isomerization of allylarene to 1‐propenylarene favors the E isomer and proceeds with quantitative conversion. The arylation takes place through oxidative cross‐coupling of allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp 2 )–H activation and represents a new method for the synthesis of 1,1‐disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp 2 )–H activation and multiple intermolecular 1,2‐, 1,3‐, and 2,3‐hydride shifts. These methods represent new approaches to the functionalization of olefins, and the mechanistic investigations could be helpful for the discovery and design of new strategies for olefin functionalization.