Visible‐Light‐Induced 1,3‐Aminopyridylation of [1.1.1]Propellane with N‐Aminopyridinium Salts

Abstract

With the aid of an electron donor−acceptor (EDA) complex, we have successfully achieved the strain‐release aminopyridiylation of [1.1.1]propellane employing N‐aminopyridinium salts as bifunctional reagents, which allows the direct installation of amino and pyridyl groups onto bicyclo[1.1.1]pentane (BCP) frameworks in the absence of an external photocatalyst. This approach exhibits a broad range of scope to afford 1,3‐aminopyridylated BCPs under mild and metal‐free conditions. The robustness of this method is highlighted by the late‐stage modification of structurally complex biorelevant molecules. Moreover, this strategy could be extended to P‐ and CF 3 radicals for the unprecedented incorporation of these functional groups across the BCP core, offering the option of divergence via a three‐component assembly. This practical method lays the foundation for the straightforward construction of new valuable C4‐pyridine‐containing BCP chemical entities, which significantly expand the scope of BCP‐type bioisosteres for broad applications in drug discovery.