Visible-Light-Driven Anti-Markovnikov Hydrocarboxylation of Acrylates and Styrenes with CO_(2)  

作　　者：He Huang Jian-Heng Ye Lei Zhu Chuan-Kun Ran Meng Miao Wei Wang Hanjiao Chen Wen-Jun Zhou Yu Lan Bo Yu Da-Gang Yu 

机构地区：[1]Key Laboratory of Green Chemistry&Technology of Ministry of Education,College of Chemistry,Analytical&Testing Center,Sichuan University,Chengdu 610064 [2]School of Chemistry and Chemical Engineering,Chongqing University,Chongqing 400030 [3]College of Chemistry,and Institute of Green Catalysis,Zhengzhou University,Zhengzhou 450001

出　　处：《CCS Chemistry》2021年第6期1746-1756,共11页中国化学会会刊（英文）

基　　金：Financial support was provided by the the National Natural Science Foundation of China(nos.21822108,21822303,21801176,21772129,and 21772020);the Fok Ying Tung Education Foundation(no.161013);Sichuan Science and Technology Program(nos.2019YJ0379 and 20CXTD0112);the Fundamental Research Funds for the Central Universities.

摘　　要：Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.

关 键 词：visible light carbon dioxide chargetransfer complex anti-Markovnikov selectivity CARBOXYLATION 

分 类 号：O62[理学—有机化学]