Abstract
Remote boronate rearrangement of boronic acids to C═N bonds is a valuable in synthetic chemistry. Conventional approaches are constrained by the need to pre-install specialized directing groups onto the starting materials. Here, we report a lactam-driven dynamic directing strategy, achieving 1,5- and 1,4-boronate rearrangements. The strategy circumvents the need for substrate pre-activation procedures, successfully overcoming a challenge in the functionalization of inactive C = N bonds to N-alkyl anilines and 3-aryl quinoxalinones. Comprehensive mechanistic investigations unveil three transformative insights: (i) Lactam leverages boron activation to C = N bonds through tetracoordinate boron species; (ii) the 1,5-boronate rearrangement to N-alkyl anilines is favored via an eight-membered boronate complex, as supported by density functional theory (DFT) studies; (iii) a catalyst-free 1,4-boronate rearrangement pathway operates through HFIP-stabilized tetracoordinate boron intermediates. This lactam-enabled boronate rearrangements offers a methodology with transformative potential.
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Data availability
The data generated in this study are provided in the Supplementary Information file. For the experimental procedures, data of NMR and HRMS analysis and computational details, see the Supplementary Information file. The computational data for each intermediate are provided in Supplementary Data 1. The list of XYZ coordinates for each structure are supplied as. zip files in Supplementary Data 3–6. The X-ray crystallographic coordinates for structures reported in this study are provided in Supplementary Data 2 and 7 and have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers 2441557 and 2341146. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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Acknowledgements
The authors (J.L., X. L., Z.-G.X., Z.-Z.C.) would like to thank Chongqing talents Foundation Project (cstc2022ycjh-bgzxm0170, cstc2022ycjh-bgzxm0170-1 and cstc2024ycjh-bgzxm0134), the Natural Science Foundation Project of CQ CSTSC (CSTB2024NSCQ-LZX0049 and CSTB2024NSCQMSX0917), Science and Technology Research Program of Chongqing Municipal Education Commission (KJQN202401347, KJQN202201302, KJZD-K202501310 and KJZD-M202401303), and Chongqing University of Arts and Sciences: Program for Talents Introduction (R2022YX07), the Natural Science Foundation Project of Yongchuan (2023yc-jckx20074 and 2025yc-cxfz10073).
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J.L. conceived the project and designed experiments. J.X. performed experiments and prepared the supplemental information. W.Y. participated in the data collection. J.L., X.L., Z.-G.X., and H. L. prepared this manuscript. Z.-Z.C. and H.L. supervised the project. All authors discussed the results and commented on the manuscript.
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Lei, J., Xu, J., Li, X. et al. Lactam enables remote boronate rearrangements to C═N bonds. Commun Chem (2026). https://doi.org/10.1038/s42004-026-01890-2
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DOI: https://doi.org/10.1038/s42004-026-01890-2
