Pd-Catalyzed Asymmetric Dearomative Heck/Tsuji-Trost Difunctionalization of Naphthalenes

Dearomative reactions represent one of the crucial strategies for constructing molecular complexity, while the asymmetric 1,4-difunctionalization of naphthalenes, which enables efficient construction of two distal chiral centers, requires further exploration. Herein, we report a Pd-catalyzed asymmetric dearomative Heck/Tsuji-Trost reaction, which achieves the 1,4-difunctionalization of the non-activated naphthalenes for the synthesis of a series of spirocyclic products bearing two distal chiral centers. Through the employment of the new chiral sulfinamide phosphine ligand featuring bulky steric hindrance, the reaction system exhibits excellent regio-, enantio-, and diastereoselectivity. 4-Aminospirocyclohexene oxindoles with diverse functional groups were obtained in moderate to excellent yields with good to excellent enantioselectivity. The reaction proceeds under mild conditions with versatile transformations of the products. Moreover, a plausible reaction mechanism was proposed based on the mechanistic studies.