文献类型：期刊文献

中文题名：三线态能量转移促进的自由基链式烯烃氢芳基化反应研究

英文题名：Research of Triplet Energy Transfer Enabled Radical-Chain Hydroarylation of Alkenes

作者：郭仕勋[1];王卫[2];张永强[1]

机构：[1]华东理工大学药学院,中国上海200237;[2]亚利桑那大学药理学和毒理学系,美国图森AZ85721-0207

年份：2025

卷号：45

期号：5

起止页码：1716

中文期刊名：有机化学

外文期刊名：Chinese Journal of Organic Chemistry

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001515642600017)】；北大核心:【北大核心2023】；

基金：Project supported by the National Natural Science Foundation of China (No. 22171080) and the Natural Science Foundation of Shanghai (No. 23ZR1417200) .

语种：中文

中文关键词：三线态能量转移;卤原子转移;烯烃氢芳基化;自由基链式反应;反马氏加成

外文关键词：triplet energy transfer;halogen-atom transfer;hydroarylation of alkenes;radical chain reaction;anti-Markovnikov addition

摘要：以碘代芳烃为芳基供体,报道了一例三线态能量转移促进的自由基链式烯烃氢芳基化反应.该反应条件绿色温和,表现出较高的反应效率,良好的官能团兼容性、底物适用性,优异的反马氏加成区域选择性,且可有效放大至克级规模.炔烃或复杂烯烃底物可有效参与.原位生成的硅自由基通过卤原子转移促进芳基自由基生成是反应得以发生的关键.通过底物设计,该反应亦可应用于四氢喹啉酮药效骨架的合成.当反应在分子内发生时,也可使用相对惰性的溴代芳烃为芳基供体.同时,初步探索了黄原酸苯酯作为芳基供体进行反应的可行性.
A radical chain hydroarylation of alkenes enabled by triplet energy transfer using aryl iodides as aryl donor rea-gents was reported.The reaction is mild and green,displays high reaction efficiency,good functional group compatibility and substrate applicability,excellent anti-Markovnikov selectivity and could be easily scaled-up to gram scales.Alkynes and com-plex alkenes were amendable.The halogen-atom transfer(XAT)promoted by in-situ generated silyl radical is crucial for the transformation.The application of the reaction in the synthesis of pharmceutiacally-relavant tetrahydroquinoline scaffold has been also demonstrated via rational design of the substrate.When the reaction occurs intramolecularly,relatively inert aryl bromide could serve as aryl donor.Meanwhile,the feasibility of phenyl xanthate as alternative aryl donor reagent was also preliminarily probed.