Recent Advances in the Light-Driven One-Step Synthesis of Dual Carbon-Substituted Bicyclo[1.1.1]pentanes

doi:10.6023/cjoc202601034

Abstract

Bicyclo[1.1.1]pentane (BCP) derivatives with dual carbon substitutions have gained significant importance in medicinal chemistry and material science due to their distinctive three-dimensional structure and rigidity. However, conventional synthetic methods face considerable challenges in preparing BCP derivatives bearing specific functional groups, including multi-step procedures, low yields, and harsh reaction conditions, which severely hinder their large-scale production and in-depth investigation. Therefore, the development of eco-friendly and efficient synthetic approaches is urgently needed. This review systematically summarizes recent advances in the one-step synthesis of dual carbon-substituted BCPs, with a focus on two major strategies: photocatalysis and photoinduction. It provides a detailed discussion on the selection of photocatalysts, substrate scope and functional group compatibility, as well as underlying reaction mechanisms. Building on current achievements, this review summarizes the future prospects of photocatalysis in synthesizing BCP derivatives, discusses the existing challenges, and proposes potential research directions, thereby offering a comprehensive reference framework for researchers in related fields.

Key words: photocatalysis, one-step, double carbon substitution, bicyclo[1.1.1]pentane (BCP), radical coupling

Cite this article

An Chen, Zeyi Wang, Wanmei Li, Jun Xu. Recent Advances in the Light-Driven One-Step Synthesis of Dual Carbon-Substituted Bicyclo[1.1.1]pentanes[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2177-2192.

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Fig. & Tab. 16

Scheme 1. Stepwise synthesis of bicarbon-substituted bicyclo[1.1.1]pentanes

Scheme 2. Dual nickel/photoreduction-catalyzed difunctionalization of [1.1.1]propellane

Scheme 3. Photocatalytic heteroaryl fluoroalkylation of [1.1.1]propellane

Scheme 4. Photocatalytic alkylamination of [1.1.1]propellane

Scheme 5. Photocatalytic Minisci-type multicomponent synthesis of 1-(halo)alkyl-3-heteroarylbicyclo[1.1.1]pentanes

Scheme 6. Synthesis of 1,3-diheteroarylbicyclo[1.1.1]pentanes via photocatalytic diheteroarylation reactions

Scheme 7. Metal-copper-photocatalyzed synergistic alkynylation of [1.1.1]propellane

Scheme 8. Visible light-induced synthesis of 3-heteroarylbicyclo[1.1.1]pentane-1-acetates

Scheme 9. Metal-free catalyst photooxidation-reduction four-component synthesis of 1,3-functionalized trifluoromethylbicyclo[1.1.1]pentane derivatives

Scheme 10. Synthesis of heteroaryl compounds containing cyanoisopropylbicyclo[1.1.1]pentane moieties by an energy transfer process

Scheme 11. Visible light induced [1.1.1]propellane direct perfluoroalkylation/isoaromatization reaction

Scheme 12. Photo-activated multicomponent synthesis of alkylheteroarylbicyclo[1.1.1]pentanes via the XAT strategy

Scheme 13. Metal-, oxidant- and additive-free multicomponent synthesis of alkylheteroarylbicyclo[1.1.1]pentanes

Scheme 14. Light-induced three-component radical coupling reaction for rapid synthesis of benzophenone-type bioisoforms

Scheme 15. Visible light-induced benzyl alcohol functionalization of [1.1.1]propellane

Scheme 16. Photo-induced synthesis of unnatural α-amino acids containing 1,3-disubstituted bicyclo[1.1.1]pentane structures

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