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Asymmetric construction of atropisomeric biaryls via a redox neutral cross-coupling strategy

Nature Catalysis volume 2, pages 314–323 (2019)Cite this article

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Abstract

Atropisomerically enriched biaryl frameworks are ubiquitous in many fields of chemistry. Enantioselective aryl–aryl cross-coupling provides the most straightforward entry to atropisomeric biaryls, with remarkable application potential in the field of chemical science. However, their development is hindered due to the lack of convenient and pragmatic protocols. Here, we report a method for the asymmetric synthesis of a myriad of 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN) and 1,1’-binaphthyl-2,2’-diamine (BINAM) derivatives in excellent yields and enantioselectivities via a redox-neutral cross-coupling protocol. Two complementary systems were devised employing a chiral phosphoric acid–salt complex or Ni(OTf)2/chiral bis(oxazoline) ligand catalytic system for accessing atropisomeric NOBIN and BINAM derivatives, respectively. This work provides an alternative avenue to enantioenriched biaryls, and provides the capability to explore the synthetic and catalytic potentials of NOBIN- and BINAM-based frameworks.

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Fig. 1: Axially chiral biaryl molecules and reaction development.
Fig. 2: Substrate generality for CPA-salt catalysed asymmetric cross-coupling.
Fig. 3: Substrate scope of BINAM derivatives via Ni(OTf)2/SaBOX-catalysed asymmetric cross-coupling.
Fig. 4: Substrate scope of NOBIN derivatives via Ni(OTf)2/SaBOX-catalysed asymmetric cross-coupling.
Fig. 5: Synthetic transformations and mechanistic studies.
Fig. 6: Plausible mechanism for Ni-catalysed asymmetric cross-coupling.

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Data availability

The X-ray crystallographic coordinates for structures of 3a-2 and 5o reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers CCDC 1846849 (3a-2) and 1846841 (5o). These data can be obtained free of charge from http://www.ccdc.cam.ac.uk/data_request/cif. Experimental procedures and characterization of the new compounds are available in the Supplementary Information. All other data are available from the authors upon reasonable request.

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Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grants nos. 21772081, 21825105, 21702092 and 21801117), Shenzhen Nobel Prize Scientists Laboratory Project (C17213101) and Shenzhen Special Funds for the Development of Biomedicine, Internet, New Energy and New Material Industries (JCYJ20170412151701379 and KQJSCX20170328153203). We dedicate this paper to the memory of L.-R. Jin.

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  1. These authors contributed equally: Liang-Wen Qi and Shaoyu Li.

Authors and Affiliations

  1. Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen, China

    Liang-Wen Qi, Shaoyu Li, Shao-Hua Xiang, Jun (Joelle) Wang & Bin Tan

  2. Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen, China

    Shaoyu Li & Shao-Hua Xiang

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Contributions

B.T. and J.W. conceived and directed the project. L.-W.Q. and S.L. designed and performed experiments and prepared the Supplementary Information. S.-H.X. helped collect some new compounds and in analysing the data. B.T., J.W. and S.-H.X. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Jun (Joelle) Wang or Bin Tan.

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Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figures 1–5, Supplementary Tables 1–11, Supplementary References.

Compound 3a-2

Crystallographic data for compound 3a-2

Compound 5o

Crystallographic data for compound 5o

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Qi, LW., Li, S., Xiang, SH. et al. Asymmetric construction of atropisomeric biaryls via a redox neutral cross-coupling strategy. Nat Catal 2, 314–323 (2019). https://doi.org/10.1038/s41929-019-0247-1

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