Distinctive Mechanistic Scenarios and Substituent Effects of Gold(I) versus Copper(I) Catalysis for Hydroacylation of Terminal Alkynes with Glyoxal Derivatives

Density functional theory (DFT) calculations have been
conducted
to study the mechanisms, substituent effects, and the role of bases
in Au- and Cu-catalyzed hydroacylation of terminal alkyne with glyoxal
derivatives. The two reactions, despite being catalyzed by the same
group of transition metals, follow distinctive reaction mechanisms.
Through the detailed DFT calculations, insights into the mechanisms
are obtained, and the substituent effects and the role of the bases
are understood.