Neighbouring carbonyl group-assisted sequential 1,2-azide and1,4-oxygen migrations of vinyl azides leading to α-azido ketones  

作　　者：Yi Gai Yongquan Ning Paramasivam Sivaguru Xiaomeng Li Yue Zhao Jiayi Wu Xihe Bi 

机构地区：[1]Department of Chemistry,Northeast Normal University,Changchun 130024,China [2]State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin 300071,China

出　　处：《Science China Chemistry》2020年第4期460-466,共7页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China(21871043);the Department of Science and Technology of Jilin Province(20180101185JC,20190701012GH);the Fundamental Research Funds for the Central Universities(2412019ZD001).

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 and1,4-oxygen migrations.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 and1,4-oxygen migrations.

关 键 词：VINYL AZIDE AZIDE migration neighboring carbonyl group-assisted PhIF2 α-azido KETONES 

分 类 号：O621.25[理学—有机化学]