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Redox-neutral ipso/ortho alkenylcyanation of (hetero)arylboronic acid enabled by 1,4-rhodium migration and fragmentation

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Abstract

A mild, chemoselective, redox-neutral ipso/ortho alkenylcyanation of arylboronic acids with homopropargylic malononitriles via 1,4-rhodium migration and fragmentation is reported. A variety of 2-vinyl arylnitriles are obtained in good yields (51 examples, ava. 69% yields) through this strategy, which is characterized by its broad substrate scope, great functional group tolerance, and mild conditions. Mechanism studies indicate that the fragmentation is temperature dependent. The primary asymmetric exploration for the non-fragmentation product already shows promising results. The separation of the two cyano groups of homopropargylic malononitriles results in the formation of aromatic nitrile and aliphatic nitrile in one molecule, which enables the further transformations of the products.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21971074), the Natural Science Foundation of Guangdong Province (2022A1515010660, 2021A1515220024), and Natural Science Foundation of GuangZhou (202102020982). We further thank Dr. H. Jiang for technical assiatance with IR, Prof. Daniel J. Weix for the discussion and helpful suggestions about this paper. Dr. Y. Zhao from Francool Technology (Shenzhen) Co. Ltd. is gratefully acknowledged for his help with the manuscript.

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Authors and Affiliations

  1. The State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, Key Laboratory of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou, 510640, China

    Chenxia Guo, Donghui Xing, Huanfeng Jiang & Liangbin Huang

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  1. Chenxia Guo
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  2. Donghui Xing
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  3. Huanfeng Jiang
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Correspondence to Liangbin Huang.

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The Supporting Information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Redox-neutral ipso/ortho alkenylcyanation of (hetero)arylboronic acid enabled by 1,4-rhodium migration and fragmenta-tion

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Guo, C., Xing, D., Jiang, H. et al. Redox-neutral ipso/ortho alkenylcyanation of (hetero)arylboronic acid enabled by 1,4-rhodium migration and fragmentation. Sci. China Chem. 66, 2283–2291 (2023). https://doi.org/10.1007/s11426-023-1645-x

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  • DOI: https://doi.org/10.1007/s11426-023-1645-x

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