Cu(I)-Photosensitizer-Catalyzed Olefin-α-Amino Radical Metathesis/Demethylenative Cyclization of 1,7-Enynes
作者:Yun Peng、Hanyang Bao、Limeng Zheng、Yan Zhou、Qibo Ni、Xiahe Chen、Yuanqiang Li、Pucha Yan、Yun-Fang Yang、Yunkui Liu
DOI:10.1021/acs.orglett.4c00793
日期:2024.4.19
A demethylenative En-Yne radical cyclization of 1,7-enynes has been successfully developed to chemoselectively afford 3,4-dihyroquinolin-2-ones or quinolin-2-ones under the catalysis of Cu(I) photosensitizers PS3 and PS6 with different redox potentials. The preliminary mechanistic experiments revealed that the reaction underwent an unprecedented olefin-α-amino radical metathesis-type process. A reasonable
已成功开发出1,7-烯炔的去亚甲基En-Yne自由基环化,在具有不同氧化还原作用的Cu(I)光敏剂PS3和PS6的催化下化学选择性地生成3,4-二氢喹啉-2-酮或喹啉-2-酮潜力。初步机理实验表明该反应经历了前所未有的烯烃-α-氨基自由基复分解型过程。基于初步机理实验和DFT计算,提出了合理的机理来说明催化剂控制的反应化学选择性。