Metal‐Enabled Reactions of Nitrenes with Alkynes: Beyond Gold Catalysis

Abstract As versatile synthons, nitrenes have attracted great attention. Two research topics, including nitrene precursor development and nitrene‐based transformations, have been thoroughly investigated so far. Generally, different nitrene precursors under various metal catalysis have allowed for the differentiation of the reactivity of the resulting nitrene, thus enabling diverse C−H insertions, aziridinations, and sulfimidations with high reaction efficiency and reaction generality. Among the addition of nitrenes with unsaturated bonds, the reaction of nitrenes and alkynes is still in its initial stage, although various metal‐catalyzed transformations, typically, rhodium‐catalyzed sulfinamate‐derived nitrene/alkyne metalation, have been well‐developed. Two types of plausible mechanism, radical and electrophilic models, have been proposed. The simple preparation of acyl nitrenes and their enantioselective reaction with alkynes, as well as their applications in biologically interesting architectures, is of great interest. In this review, we would like to describe the reaction of nitrenes with alkynes under metal catalysis. To increase readability, this review will be presented according to mechanistic pathways and types of metal.