叔膦介导的叠氮化合物与不饱和酮的连续Staudinger/Aza-Michael加成反应合成β-氨基取代酮类化合物
收稿日期: 2019-06-06
修回日期: 2019-07-09
网络出版日期: 2019-07-17
基金资助
国家自然科学基金（No.21871088）、上海市教育发展基金会和上海市教育委员会“晨光计划”（No.16CG22）、中央高校基本科研业务费专项资金（No.21871088）资助项目.
Phosphine-Mediated Sequential Staudinger/Aza-Michael Addition of Azides with Unsaturated Ketones to Synthesize β-Amino Substituted Ketones
Received date: 2019-06-06
Revised date: 2019-07-09
Online published: 2019-07-17
Supported by
Project supported by the National Natural Science Foundation of China (No. 21871088), the Chenguang Program supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission (No. 16CG22), and the Fundamental Research Funds for the Central Universities (No. 21871088).
以叔膦为介导，水为添加剂，在1，2-二氯乙烷溶剂中，叠氮化合物与三氟甲基取代α，β-不饱和酮为原料，发生连续Staudinger/Aza-Michael加成反应.所开发反应可以中等到优秀的收率（最高96%）获得氢胺化产物，并且能够实现克级规模制备目标产物.此方法有广泛的底物范围（30个底物）.核磁共振磷谱监测实验验证了反应的启动步骤是叠氮与叔膦的Staudinger反应.
关键词： 叔膦; Staudinger反应; 氮杂Michael加成; 叠氮; 氢胺化; 烯烃
丛甜甜 , 王华敏 , 刘媛媛 , 吴海虹 , 张俊良 . 叔膦介导的叠氮化合物与不饱和酮的连续Staudinger/Aza-Michael加成反应合成β-氨基取代酮类化合物[J]. 有机化学, 2019 , 39(8) : 2157 -2165 . DOI: 10.6023/cjoc201906005
A phosphine-mediated Staudinger/Aza-Michael addition of azides with trifluoromethyl substituted α,β-unsaturated ketones was developed, giving hydroamination products in medium to good yields (up to 96%). The hydroamination products could be prepared on gram scale and a wide range of substrates are tolerated under the optimized reaction conditions (30 examples). 31P NMR experiments indicate that this reaction was initiated by Staudinger reaction of azide with phosphine.
Key words： phosphines; Staudinger reaction; aza-Michael addition; azides; hydroamination; alkenes
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