Cu-catalysed enantioselective radical heteroatomic S-O cross-coupling

被引:34
作者
Cheng, Yong-Feng [1 ]
Yu, Zhang-Long [1 ]
Tian, Yu [1 ]
Liu, Ji-Ren [2 ,3 ,4 ]
Wen, Han-Tao [1 ]
Jiang, Na-Chuan [1 ]
Bian, Jun-Qian [1 ]
Xu, Guo-Xiong [2 ,3 ,4 ]
Xu, Dan-Tong [1 ]
Li, Zhong-Liang [5 ]
Gu, Qiang-Shuai [5 ]
Hong, Xin [2 ,3 ,4 ]
Liu, Xin-Yuan [1 ]
机构
[1] Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen, Peoples R China
[2] Zhejiang Univ, Ctr Chem Frontier Technol, Dept Chem, State Key Lab Clean Energy Utilizat, Hangzhou, Peoples R China
[3] Beijing Natl Lab Mol Sci, Beijing, Peoples R China
[4] Westlake Univ, Sch Sci, Key Lab Precise Synth Funct Mol Zhejiang Prov, Hangzhou, Peoples R China
[5] Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Dept Chem, Shenzhen, Peoples R China
基金
中国国家自然科学基金; 国家重点研发计划;
关键词
BOND-FORMATION; TERT-ALKYLAMINES; DESYMMETRIZATION; CHEMISTRY; ELIMINATION; ALCOHOLS;
D O I
10.1038/s41557-022-01102-z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The transition-metal-catalysed cross-coupling reaction has established itself as one of the most reliable and practical synthetic tools for the efficient construction of carbon-carbon/heteroatom (p-block elements other than carbon) bonds in both racemic and enantioselective manners. In contrast, development of the corresponding heteroatom-heteroatom cross-couplings has so far remained elusive, probably due to the under-investigated and often challenging heteroatom-heteroatom reductive elimination. Here we demonstrate the use of single-electron reductive elimination as a strategy for developing enantioselective S-O coupling under Cu catalysis, based on both experimental and theoretical results. The reaction manifests its synthetic potential by the ready preparation of challenging chiral alcohols featuring congested stereocentres, the expedient valorization of the biomass-derived feedstock glycerol, and the remarkable catalytic 4,6-desymmetrization of inositol. These results demonstrate the potential of enantioselective radical heteroatomic cross-coupling as a general chiral heteroatom-heteroatom formation strategy.
引用
收藏
页码:395 / +
页数:11
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