Ring-Strain-Promoted Transformations of Bicyclo/Azabicyclo[1.1.0]butane-Derived Boronic Esters

doi:10.6023/cjoc202603021

Abstract

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

Cite this article

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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Fig. & Tab. 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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