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

: Reported is a tandem palladium-catalyzed Heck/regioselective C(sp3 )-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-alkylPdII 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-alkylPdII intermediate.