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A boryl-migratory semipinacol rearrangement

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Abstract

The semipinacol rearrangement is one of the classic yet useful synthetic tools in organic synthesis. However, semipinacol rearrangements involving heteroatom-migration are rare. Reported herein is a boryl-migratory semipinacol rearrangement of α-hydroxyallylboronates and α-hydroxypropargylboronates triggered by diverse halogen-, oxygen-, sulfur- and selenium-containing electrophiles. The protocol leads to a mild and facile access to organoborons bearing valuable functionalities. The σ (C—B) hyperconjugation is believed to be the key factor that leads to the observed exclusive chemoselectivity and enhanced reactivity. Synthetic utilities of the formed products were demonstrated.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22022114, 21971261), the Key Project of Chinese National Programs for Fundamental Research and Development (2016YFA0602900), the Guang-dong Basic and Applied Basic Research Foundation (2020A1515010624), the Fundamental Research Funds for the Central Universities (20ykzd12), the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01Y093), and the China Postdoctoral Science Foundation (2021M69360).

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Authors and Affiliations

  1. Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, 510006, China

    Dong-Hang Tan, Zhi-Hao Chen, Ling Yang, Chang-Ting Li, Fang-Hai Tu, Qingjiang Li & Honggen Wang

  2. State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin, 541004, China

    Honggen Wang

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  1. Dong-Hang Tan
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  2. Zhi-Hao Chen
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  3. Ling Yang
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Correspondence to Honggen Wang.

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Supporting information 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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Tan, DH., Chen, ZH., Yang, L. et al. A boryl-migratory semipinacol rearrangement. Sci. China Chem. 65, 746–752 (2022). https://doi.org/10.1007/s11426-021-1188-x

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