Abstract
2,2’-Dihalo-1,1’-binaphthyl compounds can introduce coordinating groups and other complex functional systems into the binaphthyl skeleton; however, their structural diversity renders preparation challenging. In this study, a streamlined approach is developed to prepare dihalobinaphthyl compounds that uses designed, easily obtained α-hydroxyl haloalkynes as the starting materials, which combine activity of haloalkynes and traceless directional hydroxyl groups. This process involves a palladium-catalysed 1,2-halo shift, electrophilic carbocyclisation, dehalogenative coupling with another α-hydroxyl haloalkyne, and halogenated electrophilic cyclisation. Density functional theory calculations shows the occurrence of 1,2-halo shift is primarily governed by the coordination of the aromatic ring in the palladium catalyst. The target 2,2’-dihalo-1,1’-binaphthyl compounds can be prepared on the gram scale, and afford a series of ligands, catalysts, and high-value binaphthyl-based materials. This method will significantly expand the synthetic toolbox for dihalobinaphthyl compounds and create possible opportunities for preparing functionally diverse binaphthalene-based architectures with tailored properties.
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The experimental data generated in this study, including detailed experimental procedures, compound characterization data, NMR spectra of new compounds, and detailed computational results, are provided in the Supplementary Information. The Cartesian coordinates data generated in this study are provided in the Source Data file. Source data are provided with this paper. Crystallographic data have been deposited in the Cambridge Crystallographic Data Centre (CCDC) under accession codes 2157875 (a1), CCDC 2404526 (2k), CCDC 2430134 (3f), and are available free of charge via http://www.ccdc.cam.ac.uk/structures. All data supporting the findings of this study are available from the corresponding author upon request. Source data are provided with this paper.
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Acknowledgements
We would like to thank the State Key Laboratory of Pulp and Paper Engineering (2022PY01), the National Natural Science Foundation of China (22571094, H.-F.J.; x2hgB5220550, H.-F.J.; 21871095, H.-F.J.), the Key-Area Research and Development Program of Guangdong Province (2020B010188001, H.-F.J.), the Foundation of the Department of Education of Guangdong Province (2019KZDXM052, Y.-B.L.; 2021KTSCX140, Y.-B.L.), Guangdong Basic and Applied Basic Research Foundation(2024A1515010323, S.-F. N.; 2025A1515011907, S.-F.N.), and the open research fund of Songshan Lake Materials Laboratory (2023SLABFN16, S.-F.N.) for their financial support. We would like to thank Editage (www.editage.cn) for English language editing.
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Y.-B.L. and H.-F.J. conceived the “Syntheses of 2,2’-dihalo-1,1’-binaphthyl compounds via palladium-catalysed 1,2-halo shift–cyclisation coupling reaction of α-hydroxyl haloalkynes.” X.-L.J. performed the experiments, collected and analysed the data, proposed reaction mechanism, and wrote the draft. S.-F.N. Y.-B.L. W.-Q.W. and H.-F.J. revised the manuscript and discussed the mechanistic details. S.-F.N. guided W.-J.Y., who performed DFT studies. All the authors have read the manuscript and agree with its content.
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Ji, X., Li, Y., Yu, Wj. et al. Syntheses of 2,2’-dihalo-1,1’-binaphthyl compounds via palladium-catalysed 1,2-halo shift–cyclisation coupling reaction of α-hydroxyl haloalkynes. Nat Commun (2026). https://doi.org/10.1038/s41467-026-72188-z
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DOI: https://doi.org/10.1038/s41467-026-72188-z
