Polycyclization Enabled by Relay Catalysis: One‐Pot Manganese‐Catalyzed C−H Allylation and Silver‐Catalyzed Povarov Reaction

Abstract In this study, a Mn I /Ag I ‐based relay catalysis process is described for the one‐pot synthesis of polycyclic products by a formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed the first example of directed C−H allylation with allenes, setting the stage for an in situ Povarov cyclization catalyzed by silver(I). The reaction proceeds with high bond‐forming efficiency (three C−C bonds), broad substrate scope, high regio‐ and stereoselectivity, and 100 % atom economy.