Copper-catalyzed 1,4-alkylcyanation of CF3-containing 1,3-enynes: alkoxy radical-mediated selective cleavage of fused azabicycles

Abstract

A copper-catalyzed 1,4-alkylcyanation of CF₃-containing 1,3-enynes with bicyclic hydroperoxides and TMSCN is described. In this cascade, the alkyl source originates from selective cleavage of a C–C bond in the fused bicyclic skeletons, enabling the successful introduction of a succinimide fragment into tetrasubstituted allenes. This reaction is characterized by mild conditions, broad substrate scope, excellent functional group tolerance, and ease of large-scale synthesis and product derivatization.