无需自由基引发剂参与实现可见光诱导Barton脱羧  

Visible light induced Barton decarboxylation free of radical initiators

作　　者：王佳鑫 付明臣 Wang Jiaxin;Fu Mingchen(Department of Chemistry,University of Science and Technology of China,Hefei 230026,China)

机构地区：[1]中国科学技术大学化学系,安徽合肥230026

出　　处：《中国科学技术大学学报》2020年第11期1403-1410,共8页JUSTC

基　　金：the USTC Research Funds of the Double First-Class Initiative(YD2060002003).

摘　　要：报道了一种可见光诱导Barton脱羧的新方法.在不需要外加自由基引发剂的条件下,可以实现一系列一级、二级、三级以及氨基酸、多肽类氧化还原性羧酸酯脱羧,而且许多含有羧基的天然产物及药物分子也可以很好地发生转化,反应条件温和、底物范围广,具有良好的收率和官能团兼容性.初步机理实验研究表明,三(三甲基硅基)硅烷在该反应体系中不仅作为氢源,同时也作为电子给体和氧化还原性羧酸作用形成电子供体-受体复合物,反应经历自由基历程.Herein,a novel protocol for visible light induced decarboxylation was reported.The method avoids the addition of radical initiators.A series of primary,secondary,and tertiary redox-active esters underwent decarboxylation efficiently,as well as amino acid and peptide derivatives.Many natural products and drug molecules containing carboxyl groups can also be transformed well.The method has mild reaction conditions,wide substrate scope,satisfactory functional group compatibility with good to excellent yields.The preliminary mechanism studies suggested that tris(trimethylsilyl)silane((TMS)3SiH)acts not only as a hydrogen source,but also as an electron donor to form electron donor-acceptor(EDA)complex with redox-active esters,and the reaction involves the radical process.

关 键 词：可见光诱导 电子供体-受体复合物 脱羧 自由基 三(三甲基硅基)硅烷 

分 类 号：O621.2[理学—有机化学]