Abstract

The development of azide migration reactions is a formidable challenge due to potential competition from side processes driven by the release of molecular nitrogen. Here, we show a novel neighbouring carbonyl group-assisted sequential 1,2-azide and 1,4-oxygen migration reaction of α-vinyl azides for the efficient preparation of a range of α-azido ketones. This represents the first transformation of α-vinyl azides into α-azido ketones. Notable features of this method are its high efficiency, broad substrate scope, excellent functional group compatibility, and high yields. The computational studies gave a key insights into the regioselective 1,2-azide and 1,4-oxygen migrations assisted by the neighbouring carbonyl group. Further conversions into a variety of nitrogen-containing compounds demonstrated the synthetic utility of the α-azido ketone products. Preliminary mechanistic studies disclosed a novel reaction mechanism involving neighbouring carbonyl group-assisted sequential 1,2-azide and 1,4-oxygen migrations.

中文翻译：

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相邻的羰基辅助的乙烯基叠氮化物的顺序1,2-叠氮化物和1,4-氧迁移导致α-叠氮基酮

摘要

由于来自分子氮释放的副反应的潜在竞争，叠氮化物迁移反应的发展是一个巨大的挑战。在这里，我们显示了α-乙烯基叠氮化物的新型相邻羰基辅助的连续1,2-叠氮化物和1,4-氧迁移反应，可有效制备一系列α-叠氮基酮。这代表了α-乙烯基叠氮化物向α-叠氮基酮的第一次转化。该方法的显着特点是效率高，基材范围广，官能团相容性好和产率高。计算研究对区域选择性的1,2-叠氮化物和1,4-氧在邻近羰基的协助下迁移提供了重要见解。进一步转化为多种含氮化合物证明了α-叠氮基酮产物的合成效用。初步的机理研究揭示了一种新颖的反应机理，涉及相邻的羰基辅助的连续1，2-叠氮化物和1，4-氧迁移。