Transition-metal-free radical relay cyclization of vinyl azides with 1,4-dihydropyridines involving a 1,5-hydrogen-atom transfer: access to α-tetralone scaffolds
Transition-metal-free radical relay cyclization of vinyl azides with 1,4-dihydropyridines involving a 1,5-hydrogen-atom transfer: access to α-tetralone scaffolds
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乙烯基叠氮化物与 1,4-二氢吡啶的过渡金属自由基中继环化涉及 1,5-氢原子转移：获得 α-四氢萘酮支架
DOI：
10.1039/d0qo01042a
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发表时间：
2020-11-21
影响因子：
5.4
通讯作者：
Liu, Xiaozu
中科院分区：
文献类型：
--
作者：
Liao, Yangzhen;Ran, Yu;Liu, Xiaozu
已经描述了使用乙烯基叠氮化物和1，4-二氢吡啶作为前体通过自由基介导的1，5-氢原子转移（HAT）过程实现的远程C（sp（3））-H官能化。在本研究中，1，4-二氢吡啶通过连续均裂ipso-C-C键和beta-C（sp（3））-H键，可以作为1，2-双自由基配体发挥作用。该反应提供了容易获得具有优异立体选择性的多种α-四氢萘酮的途径。本发明方法的实用性通过其应用于快速组装存在于呋喃类固醇中的四环支架以及合成芳族胺而进一步突出。
The remote C(sp(3))-H functionalization enabled by a radical-mediated 1,5-hydrogen-atom transfer (HAT) process using vinyl azides and 1,4-dihydropyridines as precursors has been described. In this study, 1,4-dihydropyridines can function as 1,2-diradical synthons through sequential homolytic cleavage of an ipso-C-C bond and a beta-C(sp(3))-H bond. This reaction offers facile access to a diverse range of alpha-tetralones with excellent stereoselectivity. The utility of the present method is further highlighted by its application to rapid assembly of the tetracyclic scaffold present in furanosteroids as well as the synthesis of aromatic amines.