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Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift

Nature Chemistry volume 16, pages 42–53 (2024)Cite this article

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Abstract

Asymmetric synthesis based on a metallate shift of tetracoordinate borons is an intriguing and challenging topic. Despite the construction of central chirality from tetracoordinate boron species via a 1,2-metallate shift, catalytic asymmetric synthesis of axially chiral compounds from such boron ‘ate’ complexes is an ongoing challenge. Axially chiral alkenes have received great attention due to their unique characteristics and intriguing molecular scaffolds. Here we report an enantioselective nickel-catalysed strategy for the construction of axially chiral alkenes via a 1,3-metallate shift of alkynyl tetracoordinate boron species. The chemoselectivity, regioselectivity and atroposelectivity can be regulated and well-controlled from readily accessible starting materials with a cheap transition-metal catalyst. Downstream transformations indicate the powerful conversion ability of such compounds in this protocol, and late-stage elaborations of bioactive compounds can also be achieved. Mechanistic experiments reveal that regioselective syn-addition of an aryl–Ni complex with a carbon–carbon triple bond and subsequent 1,3-phenyl migration are the two key steps for the synthesis of axially chiral alkenes.

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Fig. 1: Background, hypothesis and our strategy.
Fig. 2: Synthetic applications.
Fig. 3: Mechanistic control experiments and possible catalytic cycle.

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Data availability

The data that support the findings of this study are available within the Article and its Supplementary Information. The X-ray crystallographic coordinates for structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition no. 2243354 (51). The data can be obtained free of charge from The Cambridge Crystallographic Data Centre.

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Acknowledgements

Financial support from the National Natural Science Foundation of China (grants 21931013 and 22271105 to Q.S.) and the Natural Science Foundation of Fujian Province (grant 2022J02009 to Q.S.) is gratefully acknowledged.

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Authors and Affiliations

  1. Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry, Fuzhou University, Fuzhou, Fujian, China

    Xingxing Ma, Mengwei Tan, Luo Li, Zihao Zhong, Puhui Li, Jinchao Liang & Qiuling Song

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Contributions

Q.S. designed and directed the project. X.M. performed the experiments and developed the reactions. M.T., L.L., Z.Z., P.L. and J.L. helped with the collection of some experimental data. Q.S. and X.M. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Qiuling Song.

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Nature Chemistry thanks Chuan He and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Tables 1–16, Figs. 1–8 and starting material preparation, experimental procedures, synthetic transformations, mechanistic studies and product characterization.

Supplementary Data 1

Crystallographic data of compound 51, CCDC reference 2243354.

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Ma, X., Tan, M., Li, L. et al. Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift. Nat. Chem. 16, 42–53 (2024). https://doi.org/10.1038/s41557-023-01396-7

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