Gold-catalyzed intermolecular alkyne hydrofunctionalizations—mechanistic insights

An overview of the current state of mechanistic understanding of gold-catalyzed intermolecular alkyne hydrofunctionalization reactions is presented. Moving from the analysis of the main features of the by-now-generally accepted reaction mechanism, studies and evidences pointing out the mechanistic peculiarities of these reactions using different nucleophiles HNu that add to the alkyne triple bond are presented and discussed. The effects of the nature of the employed alkyne substrate and of the gold catalyst (employed ligands, counteranions, gold oxidation state), of additional additives and of the reaction conditions are also considered. Aim of this work is to provide the reader with a detailed mechanistic knowledge of this important reaction class, which will be invaluable for rapidly developing and optimizing synthetic protocols involving a gold-catalyzed alkyne hydrofunctionalization as a reaction step.