Oxidative Divergent Bicyclizations of 1,n‐Enynes through α‐C(sp³)–H Functionalization of Alkyl Nitriles

A new, radical‐mediated, divergent bicyclization of 1,n‐enynes by α‐C( sp 3 )–H oxidative functionalization of alkyl nitriles is described using the Sc(OTf) 3 and Ag 2 O system. The reaction allows the selective functionalization of one or two C( sp 3 )−H bonds α to the nitrile group by both oxidants and the substitution effect co‐controlled the divergent bicyclization reactions, and offers a step‐ and atom‐economical access to diverse polycycles with broad substrate scope and high selectivity. magnified image