Asymmetric radical allylation of β-keto esters with vinyl cyclopropanes by dual photoredox/nickel catalysis  

作　　者：Wen-Yuan Qu Xue-Song Zhou Wen-Jing Xiao Jia-Rong Chen 

机构地区：[1]Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction,Ministry of Education,College of Chemistry,Central China Normal University,Wuhan 430079,China [2]Wuhan Institute of Photochemistry and Technology,7 North Bingang Road,Wuhan 430083,China [3]Key Laboratory of Organo-Pharmaceutical Chemistry of Jiangxi Province,Gannan Normal University,Ganzhou 341000,China

出　　处：《Science China Chemistry》2024年第11期3807-3816,共10页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China (22171099, and 92256301);the National Key R&D Program of China (2023YFA1507203 and 2022YFA1506100);the Open Research Fund of School of Chemistry and Chemical Engineering;the Fundamental Research Funds for the Central Universities of China (CCNU24JCPT016);Henan Normal University (2021YB02);the Double-Thousand Talents Plan of Jiangxi Province (jxsq2023102004)。

摘　　要：Radical-involved allylation reactions have emerged as a powerful platform for construction of carbon-carbon and carbonheteroatom bonds, facilitating the strategic incorporation of diverse allyl moieties. Nevertheless, this burgeoning field still faces ongoing challenges, including limitations of radical precursors and coupling partners, and difficulties in achieving enantiocontrol. Herein, we report for the first time a highly enantioselective radical allylation involving β-keto esters with vinyl cyclopropanes utilizing a synergistic dual photoredox/nickel catalysis under visible light irradiation. The mild and redox-neutral catalytic protocol demonstrates an extensive substrate compatibility and good functional tolerance, providing access to enantioenriched β-keto esters featuring quaternary α-stereocenter with good yields and high enantioselectivities. Preliminary mechanistic studies have uncovered that the success of the reaction hinges on the dual roles of nickel catalyst, including in situ formation of photoredox sensitive substrate/Ni complex and the ensuing asymmetric radical addition step.

关 键 词：asymmetric allylation photoredox catalysis radical addition nickel catalysis β-keto esters vinyl cyclopropanes 

分 类 号：O621.251[理学—有机化学]