Copper-Catalyzed and Proton-Directed Selective Hydroxymethylation of Alkynes with CO2
Dr. Mei-Yan Wang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072 China
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, 350207 China
Search for more papers by this authorXin Jin
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorXiaofei Wang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorShumei Xia
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071 China
Search for more papers by this authorYue Wang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorShouying Huang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorYing Li
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorCorresponding Author
Prof. Liang-Nian He
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071 China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorCorresponding Author
Prof. Xinbin Ma
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072 China
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, 350207 China
Search for more papers by this authorDr. Mei-Yan Wang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072 China
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, 350207 China
Search for more papers by this authorXin Jin
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorXiaofei Wang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorShumei Xia
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071 China
Search for more papers by this authorYue Wang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorShouying Huang
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorYing Li
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorCorresponding Author
Prof. Liang-Nian He
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071 China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072 China
Search for more papers by this authorCorresponding Author
Prof. Xinbin Ma
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072 China
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, 350207 China
Search for more papers by this authorGraphical Abstract
A protic switch was applied into the newly developed copper-catalyzed hydroxymethylation of alkynes with CO2. Allylic alcohols and β-chiral branched alkyl alcohols were selectively delivered with high levels of Z/E, regio-, and enantioselectivity.
Abstract
An intriguing strategy for copper-catalyzed hydroxymethylation of alkynes with CO2 and hydrosilane was developed. Switched on/off a proton source, for example, tBuOH, direct hydroxymethylation and reductive hydroxymethylation could be triggered selectively, delivering a series of allylic alcohols and homobenzylic alcohols, respectively, with high levels of Z/E, regio- and enantioselectivity. Such a selective synthesis is attributed to the differences in response of vinylcopper intermediate to proton and CO2. The protonation of vinylcopper species is demonstrated to be prior to hydroxymethylation, thus allowing a diversion from direct alkyne hydroxymethylation to reductive hydroxymethylation in the presence of suitable proton.
Supporting Information
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Citing Literature
February 19, 2021
Pages 3984-3988
