Evano G, Jouvin K, Theunissen C, Guissart C, Laouiti A, Tresse C, Heimburger J, Bouhoute Y, Veillard R, Lecomte M, Nitelet A, Schweizer S, Blanchard N, Alayrac C, Gaumont A-C
Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium.
Chem Commun (Camb). 2014 Sep 11;50(70):10008-18. doi: 10.1039/c4cc03198a.
This is not breaking news: copper acetylides, readily available polymeric rock-stable solids, have been known for more than a century to be unreactive species and piteous nucleophiles. This lack of reactivity actually makes them ideal alkyne transfer reagents that can be easily activated under mild oxidizing conditions. When treated with molecular oxygen in the presence of simple chelating nitrogen ligands such as TMEDA, phenanthroline or imidazole derivatives, they are smoothly oxidized to highly electrophilic species that formally behave like acetylenic carbocations and can therefore be used for the mild and practical alkynylation of a wide range of nitrogen, phosphorus and carbon nucleophiles.
乙炔铜，这种易于获取的、聚合物状的、具有岩石般稳定性的固体，在一个多世纪以来一直被认为是不活泼的物种和可怜的亲核试剂。实际上，这种缺乏反应活性的特性使它们成为理想的炔基转移试剂，能够在温和的氧化条件下轻松被活化。当在简单的螯合氮配体（如四甲基乙二胺、菲咯啉或咪唑衍生物）存在的情况下用分子氧处理时，它们会顺利地被氧化为高度亲电的物种，这些物种在形式上类似于炔基碳正离子，因此可用于多种氮、磷和碳亲核试剂的温和且实用的炔基化反应。
