Photocatalytic vinyl radical-mediated multicomponent 1,4-/1,8-carboimination across alkynes and olefins/(hetero)arenes  

作　　者：Shan-Shan Li Yu-Shi Jiang Xue-Ling Luo Xuming Ran Yuqiang Li Dong Wu Cheng-Xue Pan Peng-Ju Xia 

机构地区：[1]School of Chemistry and Pharmaceutical Sciences,Guangxi Normal University,Guilin,541004,China [2]Shanghai Artificial Intelligence Laboratory,Shanghai,200433,China [3]The Institute for Advanced Studies,Wuhan University,Wuhan,430064,China

出　　处：《Science China Chemistry》2024年第2期558-567,共10页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (22101059);the Guangxi Natural Science Foundation of China (2023GXNSFBA026275);the Innovation Project of Guangxi Graduate Education (YCSW2023125);partially supported by the National Key R&D Program of China (2022ZD0160100);in part by Shanghai Committee of Science and Technology(21DZ1100100)。

摘　　要：We developed a highly selective and efficient multicomponent transformation by utilizing alkynes and olefins/(hetero)arenes through photoinduced energy-transfer catalysis.The reaction involves the formation of three distinct chemical bonds,namely C(sp~3)–C(sp~2),C(sp~2)–C(sp~3),and C(sp~3)–N,in a single coordinated manner.The strategy used a vinyl radical-mediated radical relay approach under mild conditions,exhibiting a broad substrate scope(>70 examples),excellent functional-group tolerance,and remarkable regio-and anti-stereoselectivity.Through the utilization of a combination of experimental techniques and density functional theory(DFT),we delved deeper into the mechanistic intricacies of this distinctive system.Results revealed that the selective radical addition to electron-deficient alkynes,rather than olefins,was governed by the inherent reactivity of alkyl radicals.This discovery presented a highly effective approach for the synthesis of stereodefined multisubstituted alkenes.

关 键 词：alkyne-olefin coupling DFT studies regio-and anti-stereoselectivity multisubstituted alkenes 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]