Insights into the gold(i)-catalyzed intermolecular annulations of alkynes with N-allenamides: a mechanistic DFT study

Abstract

The mechanism of Au(I)-catalyzed intermolecular annulation of 2-(1-alkynyl)-2-alken-1-one with N-allenamide was carefully elucidated using density functional theory (DFT). The reaction is initiated by the binding of the Au(I) catalyst with 2-(1-alkynyl)-2-alken-1-one rather than with N-allenamide. The key intermediate, a gold all-carbon 1,3-dipole species, is revealed to be more reactive than the gold allylic carbocation. The influence of ligands and substituents was rationally analyzed. We believe that our study will provide deeper mechanistic insights into the chemoselective reactions of alkynes with N-allenamide.