对映选择合成
烯烃
化学
立体中心
激进的
催化作用
磺酰
自由基环化
磺胺
组合化学
芳基
动力学分辨率
有机化学
烷基
作者
Xitao Li,Ling Lv,Ting Wang,Qiang‐Shuai Gu,Guoxing Xu,Zhong‐Liang Li,Ye Liu,Xinhao Zhang,Gui‐Juan Cheng,Xin‐Yuan Liu
出处
期刊:Chem
[Elsevier]
日期:2020-04-24
卷期号:6 (7): 1692-1706
被引量:61
标识
DOI:10.1016/j.chempr.2020.03.024
摘要
The asymmetric radical-initiated difunctionalization of internal alkenes, which creates two vicinal stereocenters, has been a significant synthetic challenge despite the tremendous progress achieved for terminal alkenes. This is attributable to the common stepwise mechanism that involves an initial free radical addition to the alkene in a nonstereoselective fashion. We report here the first asymmetric radical 1,2-oxysulfonylation of both terminal and internal aryl alkenes in β,γ-unsaturated ketoximes in the presence of copper(I)-cinchona alkaloid-based sulfonamide catalyst. The experimental and computational mechanistic studies collectively support a CuII-CuI mechanism featuring fast, reversible addition of sulfonyl radicals to alkenes and subsequent rate- and stereo-determining C–O bond formation, namely, a scenario under Curtin-Hammett kinetic control. The method provides a robust platform for collective synthesis of a diverse array of valuable chiral sulfonyl-containing building blocks.
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