Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants

Since the beginning of this century, homogeneous gold‐catalyzed alkyne transformations have been an active area of research in pursuit of developing efficient synthetic methodologies. This emerging area of research which at the beginning exploited the mild Lewis acid character of gold and its propensity to form π‐complex with alkyne, has been reinvigorated upon the discovery of gold‐catalyzed oxidative alkyne functionalization in 2007. The gold‐catalyzed alkyne oxidation enabled direct access to α‐oxo gold carbenes and gold alkynal complex with versatile reactivity which has been applied to achieve transformations including but not limited to oxyarylation, C−H, X−H (X=N, O) insertion, cyclization, cycloaddition, ring expansion, and various cascade reactions. This review provides a comprehensive summary of methods, applications and mechanistic insight of gold‐catalyzed oxidative alkyne functionalization by N−O/S−O/C−O bond oxidants covering the literature reports appeared since 2007.