N-Heterocyclic Carbene Catalyzed Reactions Involving Acetylenic Breslow and/or Acylazolium as Key Intermediates.

N-heterocyclic carbene (NHC) organocatalysis has been developed as a powerful tool in modern synthetic chemistry. NHC catalytic activation of ynals and alkynoic acid derivatives provided versatile reactions that involve acetylenic Breslow and/or acylazolium as key intermediates, and diverse transformations have been established for access to molecules with unique skeletons in efficient fashions. Herein we summarize the recent achievements in NHC-catalyzed reactions involving acetylenic Breslow and/or acylazolium intermediates. Different reactions belonging to three catalytic modes, including (1) conjugate additions to acetylenic Breslow derived α,β-unsaturated acylazolium intermediates, (2) β-umpolung of ynals via acetylenic Breslow intermediates, and (3) conjugate additions to acetylenic acylazolium intermediates, are emphasized with examples and plausible mechanisms cited to guide a better understanding.