Alkynyl Acylazolium: A Versatile 1,3‐Bielectrophilic 3C‐Synthon in NHC‐Organocatalysis

Abstract N ‐Heterocyclic carbene (NHC) organocatalysis has emerged as a powerful tool in the field of modern organic synthesis especially in the asymmetric construction of various cyclic skeletons. As an emerging NHC‐bound 1,3‐bielectrophilic intermediate, alkynyl acylazolium has drawn substantial attention in recent years, and has been used as a versatile 3C‐synthon in synthesizing valuable organic molecules since its discovery. In this review, focused on the different pathways for the formation of alkynyl acylazoliums from different precursors like alkynoic esters, alkynoic acids and ynals, the recent advances in the transformations and applications of alkynyl acylazoliums pioneered or developed over the last decade under NHC‐catalysis were summarized comprehensively. At the same time, the outlook for further investigation and exploration of novel reaction modes for alkynyl acylazoliums in the future was also discussed.