Journal
CHEM
Volume 6, Issue 7, Pages 1692-1706Publisher
CELL PRESS
DOI: 10.1016/j.chempr.2020.03.024
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Funding
- National Natural Science Foundation of China [21722203, 21831002, 21801120, 21803047, 21933004]
- Shenzhen Special Funds [JCYJ20170412152435366]
- Guangdong Provincial Key Laboratory of Catalysis [2020B121201002]
- Shenzhen Nobel Prize Scientists Laboratory Project [C17783101]
- SUSTech Special Fund for the Construction of High-Level Universities [G02216303]
- China Postdoctoral Science Foundation [2019M650147]
- Warshel Institute for Computational Biology funding from Shenzhen City
- Shenzhen San-Ming Project [SZSM201809085]
- Warshel Institute for Computational Biology funding from Longgang District
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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 beta,gamma-unsaturated ketoximes in the presence of copper(I)cinchona alkaloid-based sulfonamide catalyst The experimental and computational mechanistic studies collectively support a Cu-II-Cu-I 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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