过渡金属催化双环[1.1.0]丁烷的环加成反应

李雪松; 吴禹翰; 周明东; 梁吉艳; 梁永民

doi:10.7536/PC20260407

化学进展 ›› :0- DOI: 10.7536/PC20260407

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过渡金属催化双环[1.1.0]丁烷的环加成反应

李雪松 ¹^,³^,^*^,^* ,
吴禹翰 ²^,³^,^*^,^* ,
周明东 ¹ ,
梁吉艳 ² ,
梁永民 ⁴

作者信息 +

Xue-Song Li ¹^,³ ,
Yuhan Wu ²^,³ ,
Ming-Dong Zhou ¹ ,
Jiyan Liang ² ,
Yong-Min Liang ⁴

Author information +

文章历史 +

摘要

桥双环[1.1.n]烷烃作为苯环的三维电子等排体，凭借其独特的空间结构，能有效改善药物分子的代谢稳定性、水溶性与靶标选择性。高张力且电子缺陷的双环[1.1.0]丁烷是构建此类骨架的关键前体，过渡金属催化双环[1.1.0]丁烷开环及环加成反应，已成为合成桥双环[1.1.n]烷烃最具策略优势的路径之一。本文总结了利用过渡金属催化双环[1.1.0]丁烷的开环与环加成反应的最新研究进展。重点阐述了Rh、Pd、Cu、Ni等不同金属催化体系下的反应模式差异，详细分析了各类反应的条件、催化循环机理，及其在合成方面的应用性。同时，本文总结了该领域目前存在的挑战，例如开发基于丰产金属的高效催化体系与反应化学选择性与立体选择性的控制、构建协同催化体系以拓展双环烷烃的反应类型，以期为未来开发更为高效、精准的合成方法提供参考与展望。

Abstract

As three-dimensional bioisosteres of benzene, bicyclo[1.1.n]alkanes possess unique structural that can significantly enhance metabolic stability, aqueous solubility, and target selectivity of drug molecules. The highly strained and electron-deficient bicyclo[1.1.0]butane serves as a pivotal precursor for constructing these frameworks. Transition-metal-catalyzed ring-opening and cycloaddition reactions of bicyclo[1.1.0]butane have emerged as one of the most synthetically advantageous strategies for accessing bridged bicyclo[1.1.n]alkanes. This review summarizes recent advances in this area, with emphasis on the divergent reaction profiles enabled by Rh, Pd, Cu, and Ni catalysts. Detailed discussions cover reaction conditions, catalytic cycle mechanisms, and synthetic utility. Current challenges are also critically assessed, including the development of efficient catalytic systems based on earth‑abundant metals, the control of chemo- and stereoselectivity, and the design of synergistic catalytic systems to broaden the reaction scope of bicycloalkanes. These perspectives aim to inspire the future development of more efficient and precise synthetic methodologies.

关键词

双环[1.1.0]丁烷 / 过渡金属催化 / 环加成反应

Key words

bicyclo[1.1.0]butane / transition metal catalysis / cycloaddition reaction

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李雪松, 吴禹翰, 周明东, 梁吉艳, 梁永民. 过渡金属催化双环[1.1.0]丁烷的环加成反应[J]. 化学进展, , (): 0 DOI:10.7536/PC20260407

Xue-Song Li, Yuhan Wu, Ming-Dong Zhou, Jiyan Liang, Yong-Min Liang. Progress in Chemistry 0 DOI:10.7536/PC20260407

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原文顺序 | 出版日期 | 本文引用

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[1]	Baeyer A. Berichte der Deutschen chemischen Gesellschaft, 1885, 18: 2269.
[2]	Wiberg K B. Angew. Chem., Int. Ed. Engl., 1986, 25: 312.
[3]	Milligan J A, Wipf P. Nature Chem., 2016, 8: 296.
[4]	Turkowska J, Durka J, Gryko D. Chem. Commun., 2020, 56: 5718.
[5]	Zhou X, Hu Y, Huang Y, Xiong Y. Chem. Commun., 2025, 61: 23.
[6]	Liu X, He J, Lin K, Wang X, Cao H. Org. Chem. Front., 2024, 11: 6942.
[7]	Golfmann M, Walker J C L. Commun. Chem., 2023, 6: 9.
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Received	Published	Revised
2026-04-07	2026-07-24	2026-06-16
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2026-07-24

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