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

Cheng, Yong-Feng1; Yu, Zhang-Long1; Tian, Yu1; Liu, Ji-Ren2,3,4; Wen, Han-Tao1; Jiang, Na-Chuan1; Bian, Jun-Qian1; Xu, Guo-Xiong2,3,4; Xu, Dan-Tong1; Li, Zhong-Liang5; Gu, Qiang-Shuai5; Hong, Xin2,3,4; Liu, Xin-Yuan1

2022-12-01

10.1038/s41557-022-01102-z

Nature Chemistry   Impact Factor & Quartile

1755-4330

1755-4349

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.

SCI

English

NI Journal Papers

First ; Corresponding

National Key R&D Program of China["2021YFF0701604","2021YFF0701704"] ; National Natural Science Foundation of China["22025103","92256301","21831002","22001111","22001109","22271133","21873081","22122109"] ; Guangdong Innovative Program[2019BT02Y335] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Science and Technology Program["KQTD20210811090112004","Q.-S.G.; JCYJ20200109141001789"] ; Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study[SN-ZJU-SIAS-006] ; Beijing National Laboratory for Molecular Sciences[BNLMS202102] ; CAS Youth Interdisciplinary Team[JCTD-2021-11] ; Fundamental Research Funds for the Central Universities["226-2022-00140","226-2022-00224"] ; Center of Chemistry for Frontier Technologies and Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province[PSFM2021-01] ; State Key Laboratory of Clean Energy Utilization[ZJUCEU2020007]

Chemistry

Chemistry, Multidisciplinary

WOS:000905022800001

NATURE PORTFOLIO

Web of Science

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

Cheng, Yong-Feng,Yu, Zhang-Long,Tian, Yu,et al. Cu-catalysed enantioselective radical heteroatomic S-O cross-coupling[J]. Nature Chemistry,2022.

Cheng, Yong-Feng.,Yu, Zhang-Long.,Tian, Yu.,Liu, Ji-Ren.,Wen, Han-Tao.,...&Liu, Xin-Yuan.(2022).Cu-catalysed enantioselective radical heteroatomic S-O cross-coupling.Nature Chemistry.

Cheng, Yong-Feng,et al."Cu-catalysed enantioselective radical heteroatomic S-O cross-coupling".Nature Chemistry (2022).