Remote Asymmetric amination of Naphthalene-Blocked Alkynes with various amines

Abstract

In this study, we rationally designed and successfully established a versatile copper-catalyzed divergent reaction system by employing alkynyl naphthalates as key substrates. This tunable catalytic strategy exhibits distinct and controllable reaction pathways depending on the type of amine reagents: primary amines undergo a formal [4+1] annulation process to efficiently construct a variety of polycyclic pyrrole derivatives, while secondary amines selectively participate in an enantioselective ε-position substitution reaction, providing chiral alkynyl naphthylamines with high enantiopurity. The present protocol proceeds under mild reaction conditions, featuring a broad substrate scope and excellent functional group tolerance. Notably, gram-scale synthesis and diverse downstream derivatizations of the target products have been successfully achieved, which strongly validate the practicality and synthetic utility of this methodology. We anticipate that this efficient and divergent catalytic approach will serve as a powerful tool for the rapid assembly of structurally diverse polycyclic pyrrole frameworks and the asymmetric synthesis of valuable chiral alkynyl naphthylamines, thus offering a valuable platform for copper-catalyzed divergent synthesis with important implications for organic synthesis and medicinal chemistry.