Chiral Ag‐Complex Catalyzed Enantioselective <i>α</i>‐Functionalization of Cyclic Azomethine Ylides with Concomitant Remote‐Controlled Asymmetric Desymmetrization of <i>N</i>‐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.