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

In this study, a MnI /AgI -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.