Palladium‐Catalyzed Divergent Cyclopropanation by Regioselective Solvent‐Driven C(sp3)−H Bond Activation

Abstract Reported is a tandem palladium‐catalyzed Heck/regioselective C(sp 3 )−H activation reaction for the divergent synthesis of spiro‐ and fused‐cyclopropanated indolines from N ‐methallylated 2‐bromoarylamides. The regioselectivity of the C−H bond activation in the σ‐alkylPd II intermediate is controlled by the solvent used. DFT calculations suggest that the polarity of solvent molecules could influence the transition‐state energy, leading to a bifurcation of the C−H bond activation in the σ‐alkylPd II intermediate.