Neighbouring carbonyl group-assisted sequential 1,2-azide and 1,4-oxygen migrations of vinyl azides leading to α-azido ketones

• 来源期刊: 中国科学:化学（英文版）
• 年，卷（期）: 2020,（4）
• 页码范围: 460-466
• 页数: 7页
• 语种: 英文

摘要

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.