Visible-Light-Induced Selective Hydrocarboxylation of Alkynes with Formate  

可见光诱导甲酸盐参与的炔烃氢羧基化反应

作　　者：Xu Hui Jiang Huixian Kan Lei Xu Pei Zhu Xu 徐辉;蒋慧娴;阚磊;徐佩;朱旭(徐州医科大学药学院、江苏省新药研究与临床药学重点实验室,江苏徐州221004)

机构地区：[1]Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy,School of Pharmacy,Xuzhou Medical University,Xuzhou,Jiangsu 221004

出　　处：《有机化学》2024年第10期3241-3248,共8页Chinese Journal of Organic Chemistry

基　　金：江苏省特聘教授(2020)资助项目。

摘　　要：An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation of alkynes was realized with CO_(2) radical anion in-situ generated from formate as both a carbonyl source and a reductant.The collaboration between photosensitizer and hydrogen atom transfer catalyst promoted the catalytic cycle to work smoothly,giving a broad substrate scope including terminal and internal alkynes.The Giese radical addition of CO_(2) radical anion to the C—C triple bond is the key step to initiate the reaction.发展了一种绿色高效的炔烃区域选择性氢羧基化反应以构建种类丰富的丙酸衍生物.在可见光诱导条件下,甲酸盐原位产生的二氧化碳自由基负离子,既充当羧基来源,也充当还原剂,在炔烃的氢羧基化反应中扮演重要角色.光敏剂和氢原子转移催化剂的协同作用,促进该催化循环的顺利进行.各类末端和中间炔烃都能够很好地参与反应.二氧化碳自由基负离子对C-C叁键的Giese自由基加成,是引发该反应进行的关键步骤.

关 键 词：FORMATE CO_(2)radical anion HYDROCARBOXYLATION visible-light catalysis aryl propionic acids 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]