Transition Metal-Catalyzed Hydrosilylation and Boration of Methylenecyclopropanes

doi:10.6023/cjoc202509017

Abstract

Organosilicon and organoboron compounds constitute pivotal synthons in organic chemistry, exhibiting broad applications in the synthesis of pharmaceuticals, advanced materials, and natural products. Methylenecyclopropanes, as a significant class of strained cyclic compounds, feature both a highly strained cyclopropane moiety and a carbon-carbon double bond within their structure. Owing to the distinctive structure, they undergo selective ring-opening under transition-metal catalysis, thereby providing straightforward and efficient synthetic strategies for accessing structurally diverse organosilicon and organoboron compounds. This review comprehensively summarizes the recent advances in transition metal-catalyzed hydrosilylation and boration reactions of methylenecyclopropanes, with detailed discussions on their reaction mechanism, and offers perspectives on future research directions in this field.

Key words: methylenecyclopropanes, transition-metal catalysis, hydrosilylation, boration

Cite this article

Jinyu Zhang, Zhigang Lu, Zhe Liu, Cong Wang. Transition Metal-Catalyzed Hydrosilylation and Boration of Methylenecyclopropanes[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 806-816.

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Fig. & Tab. 20

Scheme 1. Transition metal-catalyzed reaction model of MCPs

Scheme 2. Rh/Pt-catalyzed ring-opening hydrosilylation of MCPs

Scheme 3. La-catalyzed hydrosilylation of ACPs

Scheme 4. Cu-catalyzed enantioselective sequential hydrosilylation of ACPs

Scheme 5. Cu-catalyzed hydrosilylation and hydroboration of ACPs

Scheme 6. Cu-catalyzed enantioselective hydrosilylation of ACPs and ACBs

Scheme 7. Ni-catalyzed stereospecific and enantioselective hydrosilylation of MCPs

Scheme 8. Pt-catalyzed diboration of MCPs

Scheme 9. Ir-catalyzed regioselective 1,n-diboration of MCPs

Scheme 10. Mechanism of Ir-catalyzed diboration of diaryl-substituted MCPs

Scheme 11. Mechanism of Ir-catalyzed 1,n-diboration of monoaryl-substituted MCPs

Scheme 12. Co-catalyzed regiodivergent ring-opening dihydroboration of ACPs

Scheme 13. Fe-catalyzed regioselective ring-opening alkenylboration of MCPs

Scheme 14. Cu-catalyzed enantioselective ring-opening diboration of ACPs

Scheme 15. Cu-catalyzed ring-opening diboration of ACPs and ACBs

Scheme 16. Cu-catalyzed aminoboration of ACPs

Scheme 17. Mechanism of Cu-catalyzed sequential hydroboration-hydroamination/ hydroaminocarbonylation of ACPs

Scheme 18. Cu-catalyzed borocarbonylation of ACPs

Scheme 19. Cu-catalyzed 1,2-alkylboration of ACPs

Scheme 20. One-pot Co- or Cu-catalyzed hydrosilylation/hydroboration of ACPs

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