Rhodium‐Catalyzed Enantioselective Oxidative [3+2] Annulation of Arenes and Azabicyclic Olefins through Twofold C−H Activation

C−H bond activation is mostly limited to ortho selectivity. Activation of both ortho and meta C−H bonds constitutes a particularly important strategy for annulation, but has rarely been studied in enantioselective systems. Reported herein is rhodium(III)‐catalyzed asymmetric [3+2] transannulation of arenes with 7‐azabenzonorbornadienes. Two distinct classes of arenes have been identified as substrates, and the coupling proceeded with high enantioselectivity and excellent diastereoselectivity through sequential activation of ortho and meta C−H bonds. In a rare case of asymmetric twofold C−H activation, rhodium(III)‐catalyzed oxidative [3+2] transannulation of two distinct classes of arenes with azabicyclic olefins occurred with high enantioselectivity to give variously substituted heterocyclic products containing two stereocenters (see scheme). The isolation of a chiral RhIII intermediate aided the elucidation of the reaction mechanism.