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Sigmatropic rearrangements of B(MIDA)-propargylic alcohols towards the diverse synthesis of α-functionalized organoborons

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Abstract

α-Functionalized organoborons are useful building blocks and key structural elements in functional molecules. Their previous synthesis relied on the famous Matteson reaction or the late-stage borylative modification of alkynes or alkenes. Recently, the synthetic transformation of borylated building blocks offers another useful strategy and is currently actively explored. We report herein that B(MIDA)-propargylic alcohols (BPAs) are a useful type of borylated building blocks. Bearing two complementary functional group handles (alkyne and hydroxyl) in close proximity, the redox-neutral [3,3] and [2,3] sigmatropic rearrangements of BPAs allow the efficient synthesis of several types of α-functionalized boronates, including α,β-unsaturated acylborons, α-S/P-substituted allenylborons, boryl-substituted thiazoles and a borylated α,β-unsaturated hydrazine, some of which are otherwise challenging targets using other synthetic methods.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22022114, 21971261), the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01Y093), and Guangdong Basic Research Center of Excellence for Functional Molecular Engineering. This work is dedicated to the 20th Anniversary of School of Pharmaceutical Sciences, Sun Yat-sen University.

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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

    Jiasheng Qian, Li-Cai Liu, Zhi-Hao Chen, Yuan Liu, Yin Li, Qingjiang Li & Honggen Wang

Authors
  1. Jiasheng Qian
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  2. Li-Cai Liu
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  3. Zhi-Hao Chen
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  4. Yuan Liu
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  5. Yin Li
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  6. Qingjiang Li
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  7. Honggen Wang
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Correspondence to Qingjiang Li or Honggen Wang.

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Conflict of interest The authors declare no conflict of interest.

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Supporting information The supporting information is available online at chem.scichina.com and 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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11426_2023_1722_MOESM1_ESM.pdf

Sigmatropic Rearrangements of B(MIDA)-Propargylic Alcohols towards the Diverse Synthesis of α-Functionalized Organoborons

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Qian, J., Liu, LC., Chen, ZH. et al. Sigmatropic rearrangements of B(MIDA)-propargylic alcohols towards the diverse synthesis of α-functionalized organoborons. Sci. China Chem. 67, 568–575 (2024). https://doi.org/10.1007/s11426-023-1722-8

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  • DOI: https://doi.org/10.1007/s11426-023-1722-8

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