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Iron-catalysed asymmetric carboazidation of styrenes

Nature Catalysis volume 4, pages 28–35 (2021)Cite this article

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Abstract

Carboazidation of olefins is an efficient process to convert hydrocarbons directly into nitrogen-containing molecules. Such chemicals find broad applications in medicine and material sciences. Despite the fast development of carboazidation reactions, asymmetric radical carboazidations are still elusive. Here, we report a radical asymmetric carboazidation of olefins via an iron-catalysed group transfer mechanism. The method affords valuable chiral halogenated organoazides from inexpensive industrial chemical feedstocks. This radical azidation reaction is supported by mechanistic studies and should inspire further development of enantioselective radical reactions.

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Fig. 1: Stereocontrol at a radical centre.
Fig. 2: Substrate scope with respective to olefins and carbon sources.
Fig. 3: Mechanistic studies.
Fig. 4: Synthetic use of the chiral azides.

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Data availability

Data relating to the characterization data of materials and products, general methods, optimization studies, experimental procedures, mechanistic studies, mass spectrometry, high-performance liquid chromatography and NMR spectra, computational studies are available in the Supplementary Information. Crystallographic data for compounds L2Fe(OTf)2, 63, 72A and 72B are available free of charge from the Cambridge Crystallographic Data Centre (CCDC) under reference numbers 1938900, 1938899, 2003644 and 2015243, respectively.

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Acknowledgements

We thank K. Ding and X.L. Hou from Shanghai Institute of Organic Chemistry, A. Studer from University of Münster, X. Wang from Lanzhou University, W. Xie from Northwest A&F University and W. Su from our institute for inspiring discussions, D. Yuan and X. Jiang from our institute for X-ray crystallography analysis. We thank G.W.A. Milne for his writing suggestions. Supported by the National Key R&D Programme of China (grant no. 2017YFA0700103), the NSFC (grant nos. 21672213, 21871258 and 21922112), the Strategic Priority Research Programme of the Chinese Academy of Sciences (grant no. XDB20000000), the Haixi Institute of CAS (grant no. CXZX-2017-P01), the Innovative Research Teams Programme II of Fujian Normal University in China (grant no. IRTL1703), the Shenzhen STIC (grant no. JCYJ20170412150343516) and the Shenzhen San-Ming Project (grant no. SZSM201809085).

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Author notes

  1. These authors contributed equally: Liang Ge, Huan Zhou, Mong-Feng Chiou.

Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences, Fuzhou, Fujian, P. R. China

    Liang Ge, Huan Zhou, Mong-Feng Chiou, Wujun Jian, Changqing Ye, Xiaoyan Li, Xiaotao Zhu, Haigen Xiong, Yajun Li & Hongli Bao

  2. Shenzhen Bay Laboratory, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, P. R. China

    Heming Jiang, Lijuan Song & Xinhao Zhang

  3. University of Chinese Academy of Sciences, Beijing, P. R. China

    Hongli Bao

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Contributions

H.B. directed the investigations and prepared the manuscript. L.G., H.Z., W.J., C.Y., X.L., X. Zhu and H.X. performed the synthetic experiments and analysed the experimental data. X. Zhang directed the calculation study and M.-F.C. completed the theoretical calculations. H.J. conducted the mass spectra studies, L.S. did the non-covalent bond interaction analysis. Y.L. double checked the data in the Supplementary Information. L.G., H.Z. and M.-F.C. contributed equally.

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Correspondence to Xinhao Zhang or Hongli Bao.

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Supplementary information

Supplementary information

Supplementary Tables 1–4, Methods, Discussion, Figs. 1–8 and references.

Supplementary Data

44 coordinate of optimized structures file as text.

Supplementary Data 1

X-ray crystal structure of iron catalyst A, L2Fe(OTf)2.

Supplementary Data 2

X-ray crystal structure of product 72B.

Supplementary Data 3

X-ray crystal structure of product 72A.

Supplementary Data 4

X-ray crystal structure of product 63.

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Ge, L., Zhou, H., Chiou, MF. et al. Iron-catalysed asymmetric carboazidation of styrenes. Nat Catal 4, 28–35 (2021). https://doi.org/10.1038/s41929-020-00551-4

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