Department of Chemistry, University of Zurich, Winterthurerstrasse 190, Zurich, CH 8057, Switzerland.
J Am Chem Soc. 2023 Jun 14;145(23):12532-12540. doi: 10.1021/jacs.3c00744. Epub 2023 May 30.
An asymmetric three-component carbosulfonylation of alkenes is presented here. The reaction, involving the simultaneous formation of a C-C and a C-S bond across the π-system, uses a dual nickel/photoredox catalytic system to produce both β-aryl and β-alkenyl sulfones in high yields and with excellent levels of stereocontrol (up to 99:1 er). This protocol exhibits a broad substrate scope and excellent functional group tolerance and its synthetic potential has been demonstrated by successful applications toward pharmacologically relevant molecules. A broad array of control experiments supports the involvement of a secondary alkyl radical intermediate generated through radical addition of a sulfonyl radical to the double bond. Moreover, stoichiometric and cross-over experiments further suggest an underlying Ni(0)/Ni(I)/Ni(III) pathway operative in these transformations.
本文提出了一种不对称的三组分烯烃碳磺酰化反应。该反应涉及通过π 体系同时形成 C-C 和 C-S 键，使用双镍/光氧化还原催化体系以高产率和优异的立体选择性（高达 99:1er）生成β-芳基和β-烯基砜。该方案具有广泛的底物范围和出色的官能团耐受性，通过成功应用于具有药理相关性的分子证明了其合成潜力。大量的对照实验支持通过磺酰基自由基的自由基加成到双键上生成仲烷基自由基中间体。此外，计量和交叉实验进一步表明，这些转化中存在潜在的 Ni(0)/Ni(I)/Ni(III) 途径。
