Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Northeast Normal University, Changchun 130024, China.
Chem Soc Rev. 2017 Nov 27;46(23):7208-7228. doi: 10.1039/c7cs00017k.
Vinyl azides are highly versatile synthons that provide access to numerous N-heterocycles and other functional groups. α-Substituted vinyl azides (azido vinylidenes) are a special class that display unique reactivity, able to react not only as azides, but also as radical acceptors, enamine-type nucleophiles, and even electrophiles, thus delivering a wide range of nitrogen-containing compounds and their derivatives. An impressive variety of intermediates - such as iminodiazonium ions, nitrilium ions, iminyl radicals, and metal enaminyl radicals - can be generated from vinyl azides and exploited in cycloadditions, C-H functionalizations, hydrolysis processes, and cascade reactions under transition metal/photoredox catalysis. In addition to presenting synthetic protocols to access vinyl azides, this Review offers a comprehensive coverage of the development of their multifaceted reactivity, and highlights their potential as versatile precursors for synthetic applications.
乙烯基叠氮化物是高度通用的合成子，可用于合成许多含氮杂环和其他官能团。α-取代的乙烯基叠氮化物（叠氮乙烯基）是一类特殊的化合物，具有独特的反应性，不仅可以作为叠氮化物反应，还可以作为自由基受体、烯胺型亲核试剂，甚至是亲电试剂，从而提供了广泛的含氮化合物及其衍生物。通过乙烯基叠氮化物可以生成各种令人印象深刻的中间体，如亚氨基二氮烯离子、腈鎓离子、亚氨基自由基和金属烯胺自由基，这些中间体可用于环加成、C-H 官能化、水解反应和在过渡金属/光氧化还原催化下的级联反应。除了提供合成乙烯基叠氮化物的方案外，本综述还全面介绍了其多方面反应性的发展，并强调了它们作为多功能前体在合成应用中的潜力。
