环张力促进的双环/氮杂双环[1.1.0]丁烷硼酸酯的转化

doi:10.6023/cjoc202603021

摘要/Abstract

双环[1.1.0]丁烷和氮杂双环[1.1.0]丁烷衍生硼酸酯(BCB-Bpins)兼具高环张力与硼官能团的独特反应活性, 其转化通常以环张力释放为核心驱动力. 系统综述了近年来BCB-Bpins转化反应的研究进展, 并将其归纳为三类主要途径: 离子型转化, 包括硼酸酯复合物参与的亲核1,2-迁移; 自由基型转化, 包括环张力释放驱动的自由基加成反应; 过渡金属催化的立体选择性转化, 重点涉及钯或铱催化下的立体选择性与不对称双官能团化反应. 结合代表性实例, 对反应设计、区域与立体选择性控制及机理认识进行了总结与讨论, 并对该领域在新型催化不对称转化和反应模式拓展方面面临的挑战与发展方向进行了展望.

关键词: 硼酸酯复合物, 释放环张力驱动的转化, 催化不对称转化

Bicyclo[1.1.0]butane- and azabicyclo[1.1.0]butane-derived boronic esters (BCB-Bpins) combine high ring strain with the versatile reactivity of organoboron groups, and their transformations are typically driven by strain release. This review summarizes recent advances in BCB-Bpin chemistry through three main pathways: ionic pathways, such as nucleophilic 1,2-shift in boronate complexes; radical approaches, including strain-release-driven additions to BCB-Bpins; and transition- metal-catalyzed stereoselective functionalizations, especially Pd- and Ir-catalyzed stereoselective and asymmetric difunctiona- lizations. Representative studies, mechanistic features, selectivity control, current challenges, and future opportunities are also discussed.

Key words: boronate complexes, ring-strain-promoted transformations, catalytic asymmetric transformations

引用此文

董天戈, 吉崇磊, 高得伟. 环张力促进的双环/氮杂双环[1.1.0]丁烷硼酸酯的转化[J]. 有机化学, 2026, 46(9): 3480-3494.

Tian-Ge Dong, Chong-Lei Ji, De-Wei Gao. Ring-Strain-Promoted Transformations of Bicyclo/Azabicyclo[1.1.0]butane-Derived Boronic Esters[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3480-3494.

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图/表 11

Figure 1. (a) Bioactive molecules containing an azetidine or cyclobutyl moiety; (b) Most commonly used methods for the synthesis of ring-strained bicyclic boronic esters; (c) Three major transformative pathways of BCB-Bpins

Scheme 1. Stereocontrolled synthesis of cyclobutyl boronic esters through radical addition to strained σ-bonds

Scheme 2. Direct observation of reactive intermediates in radical-induced 1,2-metalate rearrangement by time-resolved spectroscopy

Scheme 3. Radical addition to bicyclo[1.1.0]butyl boronic ester followed by reduction

Scheme 4. Strain-release-driven homologation of BCB-Bpin for azetidine synthesis

Scheme 5. Electrophile-induced difunctionalization of strained σ‑bonds in bicyclo[1.1.0]butyl boronate complexes

Scheme 6. Strain-release-driven synthesis of borylated cyclobutanes and cyclopropanes

Scheme 7. Pd-catalyzed stereoselective 1,2-metalate shift of ring-strained boronate complexes

Scheme 8. Ir-catalyzed asymmetric functionalization of C—C σ-bonds via 1,2-metalate migration

Scheme 9. Asymmetric synthesis of atropisomers containing cyclobutane boronic esters

Scheme 10. Catalytic asymmetric functionalization of bicyclo[1.1.0]butane boronic esters enabled by 1,2-oxygen migration

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