Chiral Ag‐Complex Catalyzed Enantioselective α‐Functionalization of Cyclic Azomethine Ylides with Concomitant Remote‐Controlled Asymmetric Desymmetrization of N‐Arylmaleimides and Cyclopentene‐1,3‐diones

Comprehensive Summary The asymmetric cycloaddition reactions of 1,3‐fused cyclic azomethine ylides have been extensively studied, but the non‐cyclic α ‐functionalization of these compounds remains unexplored. Herein, an efficient combination of the catalytic enantioselective non‐cyclic α ‐functionalization of 1,3‐fused cyclic azomethine ylides and the remote‐controlled asymmetric desymmetrization of N ‐arylmaleimides and cyclopentene‐1,3‐diones has been achieved with a catalyst system consisting of a chiral P,N ‐ferrocene ligand and AgNO 2 . This reaction allowed for the synthesis of a series of enantioenriched 3,4‐dihydroisoquinoline derivatives bearing multiple stereogenic elements/centers with good yields and stereoselectivities. The practicality of this method was demonstrated by gram‐scale synthesis and derivatizations of the products.