Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C-O Bond Coupling of Acyl Radicals

Yu, Zhang-Long1,2,3; Cheng, Yong-Feng2,3; Liu, Ji-Ren2,3; Yang, Wu2,3; Xu, Dan-Tong2,3; Tian, Yu2,3; Bian, Jun-Qian2,3; Li, Zhong-Liang2,3; Fan, Li-Wen2,3; Luan, Cheng4,5; Gao, Ang4,5; Gu, Qiang-Shuai4,5; Liu, Xin-Yuan2,3

2023-03-01

10.1021/jacs.3c00671

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Impact Factor & Quartile

0002-7863

1520-5126

Transition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemoand stereocontrol challenging. Herein, we describe Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling of acyl radicals. This reaction is compatible with (hetero)aryl and alkyl aldehydes and, more importantly, displays a very broad scope of challenging alcohol substrates, such as 2,2-disubstituted 1,3-diols, 2-substituted-2-chloro-1,3-diols, 2-substituted 1,2,3-triols, 2 -substituted serinols, and meso primary 1,4-diols, providing enantioenriched esters characterized by challenging acyclic tetrasubstituted carbon stereocenters. Partnered by one-or two-step follow-up transformations, this reaction provides a convenient and practical strategy for the rapid preparation of chiral C3 building blocks from readily available alcohols, particularly the industrially relevant glycerol. Mechanistic studies supported the proposed C-O bond coupling of acyl radicals.

SCI

English

Corresponding

National Key R&D Program of China["2021YFF0701604","2021YFF0701704"] ; Na-tional Natural Science Foundation of China["22025103","92256301","21831002","22001109","22271133","22001111"] ; Guangdong Innovative Program[2019BT02Y335] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Science and Technology Program["KQTD 2 0 2 1 0 8 1 1 0 9 0 1 1 2 0 0 4","JCYJ20200109141001789"]

Chemistry

Chemistry, Multidisciplinary

WOS:000950578800001

AMER CHEMICAL SOC

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Yu, Zhang-Long,Cheng, Yong-Feng,Liu, Ji-Ren,et al. Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C-O Bond Coupling of Acyl Radicals[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023.

Yu, Zhang-Long.,Cheng, Yong-Feng.,Liu, Ji-Ren.,Yang, Wu.,Xu, Dan-Tong.,...&Liu, Xin-Yuan.(2023).Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C-O Bond Coupling of Acyl Radicals.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.

Yu, Zhang-Long,et al."Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C-O Bond Coupling of Acyl Radicals".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023).