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Construction of axial chirality via asymmetric radical trapping by cobalt under visible light

Nature Catalysis volume 5, pages 788–797 (2022)Cite this article

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Abstract

The 3d metals have been identified as economic and sustainable alternatives to palladium, the frequently used metal in transition-metal-catalysed cross-couplings. However, cobalt has long stood behind its neighbouring elements, nickel and copper, in asymmetric radical couplings owing to its high catalytic activity in the absence of ligands resulting in unfavourable un-asymmetric background reactions. Here we disclose an asymmetric metallaphotoredox catalysis (AMPC) strategy for the dynamic kinetic asymmetric transformation of racemic heterobiaryls, which represents a visible-light-induced, asymmetric radical coupling for the construction of axial chirality. This success can also be extended to the reductive cross-coupling variant featuring the use of more easily available organic halide feedstocks. The keys to these achievements are the rational design of a sustainable AMPC system that merges asymmetric cobalt catalysis with organic photoredox catalysis in combination with the identification of an efficient chiral polydentate ligand.

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Fig. 1: Design blueprint for AMPC-enabled DYKAT of racemic heterobiaryls.
Fig. 2: Probe the feasibility of the reactivity of cobalt/photoredox-catalysed radical coupling.
Fig. 3: Condition optimization for the AMPC-enabled DYKAT reaction.
Fig. 4: Substrate scope of the AMPC-enabled radical DYKAT.
Fig. 5: Substrate scope of AMPC-enabled radical DYKAT via reductive coupling.
Fig. 6: Demonstrations of the utilities of the developed methodology.
Fig. 7: Mechanistic investigations.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2124717 (3g) and 2124714 (Me-3k). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Data related to materials and methods, optimization of conditions, experimental procedures, mechanistic experiments, DFT calculations, HPLC spectra and spectra are provided in the Supplementary information. All data are available from the corresponding authors upon reasonable request.

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Acknowledgements

We thank J. Zhang and Soochow Chirally-Chem Co., Ltd for providing ligands, M.-Y. Liu for determination of circularly polarized luminescence signal (|glum|) and F.-F. Pan for the X-ray single-crystal diffraction analysis, and J.-R. Chen and Y. Cheng for helpful discussions. X.Q. acknowledges the supercomputing system in the Supercomputing Center of Wuhan University. This work was supported by the National Natural Science Foundation of China (grant nos. 91956201, 21820102003 and 21772053 to W.-J.X. and 21822103 and 21772052 to L.-Q.L.), the Natural Science Foundation of Hubei Province (grant No. 2017AHB047 to W.-J.X.) and the International Joint Research Center for Intelligent Biosensing Technology and Health.

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Author notes

  1. These authors contributed equally: Xuan Jiang, Wei Xiong.

Authors and Affiliations

  1. CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, China

    Xuan Jiang, Wei Xiong, Fu-Dong Lu, Yue Jia, Qian Yang, Li-Yuan Xue, Liang-Qiu Lu & Wen-Jing Xiao

  2. Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, China

    Shuang Deng & Xiaotian Qi

  3. Department of Chemistry, The University of Kansas, Lawrence, KS, USA

    Jon A. Tunge

  4. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, China

    Liang-Qiu Lu

  5. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, China

    Wen-Jing Xiao

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Contributions

L.-Q.L. and W.-J.X. directed the project and wrote the manuscript with input from all other authors. Under the guidance of L.-Q.L. and W.-J.X., X.J. and W.X. developed the methods and designed and performed the synthetic and mechanistic experiments with the help of F.-D.L, Y.J., Q.Y. and L.-Y.X. In addition, S.D. performed the DFT calculations under the guidance of X.Q. J.A.T. gave many helpful suggestions and helped to revise this manuscript. All the authors participated in the discussion and preparation of the manuscript.

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Correspondence to Liang-Qiu Lu or Wen-Jing Xiao.

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Nature Catalysis thanks Dong Wang, Pedro Merino and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Discussion, references, Tables 1–15 and Figs. 1–24.

Supplementary Data 1

Computational data for Cartesian coordinates of optimized structures.

Supplementary Data 2

Crystallographic data for compound 3g.

Supplementary Data 3

Crystallographic data for compound Me-3k.

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Jiang, X., Xiong, W., Deng, S. et al. Construction of axial chirality via asymmetric radical trapping by cobalt under visible light. Nat Catal 5, 788–797 (2022). https://doi.org/10.1038/s41929-022-00831-1

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