过渡金属催化亚甲基环丙烷的硅氢化和硼化反应

doi:10.6023/cjoc202509017

摘要/Abstract

有机硅化合物和有机硼化合物是有机化学中重要的合成子, 在药物、材料及天然产物的合成中具有广泛应用. 亚甲基环丙烷作为一类重要的张力环化合物, 因其结构中具有环张力较大的环丙烷模块和碳碳双键, 在过渡金属催化下会发生选择性开环, 从而为结构多样的有机硅和有机硼化合物提供高效、精准的合成途径. 系统综述了近年来过渡金属催化亚甲基环丙烷的硅氢化和硼化反应研究进展, 重点探讨了其反应机理, 并对未来发展趋势进行了展望.

关键词: 亚甲基环丙烷, 过渡金属催化, 硅氢化, 硼化

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

引用此文

张晋瑜, 卢志刚, 刘喆, 王聪. 过渡金属催化亚甲基环丙烷的硅氢化和硼化反应[J]. 有机化学, 2026, 46(3): 806-816.

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.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 20

图式1. 过渡金属催化MCPs的反应模式

Scheme 1. Transition metal-catalyzed reaction model of MCPs

图式2. 铑/铂催化MCPs的开环硅氢化反应

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

图式3. 镧催化ACPs的硅氢化反应

Scheme 3. La-catalyzed hydrosilylation of ACPs

图式4. 铜催化ACPs的对映选择性连续硅氢化反应

Scheme 4. Cu-catalyzed enantioselective sequential hydrosilylation of ACPs

图式5. 铜催化ACPs的硅氢化及硼氢化反应

Scheme 5. Cu-catalyzed hydrosilylation and hydroboration of ACPs

图式6. 铜催化ACPs及ACBs的对映选择性硅氢化反应

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

图式7. 镍催化MCPs的立体专一性和对映选择性开环硅氢化反应

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

图式8. 铂催化MCPs的双硼化反应

Scheme 8. Pt-catalyzed diboration of MCPs

图式9. 铱催化MCPs的区域选择性1,n-双硼化反应

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

图式10. 铱催化双芳基亚甲基环丙烷的双硼化反应机理

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

图式11. 铱催化单芳基亚甲基环丙烷的-双硼化反应机理

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

图式12. 钴催化ACPs的区域发散性开环双硼氢化反应

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

图式13. 铁催化MCPs的区域选择性开环烯基硼化反应

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

图式14. 铜催化ACPs的对映选择性开环双硼化反应

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

图式15. 铜催化ACPs和ACBs的开环双硼化反应

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

图式16. 铜催化ACPs的氨基硼化反应

Scheme 16. Cu-catalyzed aminoboration of ACPs

图式17. 铜催化ACPs的连续硼氢化-氢氨化/氢酰胺化机理

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

图式18. 铜催化ACPs的硼羰基化反应

Scheme 18. Cu-catalyzed borocarbonylation of ACPs

图式19. 铜催化ACPs的1,2-烷基硼化反应

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

图式20. 钴/铜催化ACPs的一锅法硅氢化/硼氢化反应

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

参考文献 24

[1]	(a) Nakamura, I.; Yamamoto, Y. Adv. Synth. Catal. 2002, 344, 111.
	(b) Brandi, A.; Cicchi, S.; Cordero, F. M.; Goti, A. Chem. Rev. 2003, 103, 1213.
	(c) Pellissier, H. Tetrahedron 2014, 70, 4991.
	(d) Fumagalli, G.; Stanton, S.; Bower, J. F. Chem. Rev. 2017, 117, 9404.
[2]	(a) Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117.
	(b) Cohen, Y.; Cohen, A.; Marek, I. Chem. Rev. 2021, 121, 140.
[3]	(a) Franz, A. K.; Wilson, S. O. J. Med. Chem. 2013, 56, 388.
	(b) Gai, L. Z.; Mackc, J.; Lua, H.; Nyokongc, T.; Li, Z. F.; Kobayashi, N.; Shen, Z. Coord. Chem. Rev. 2015, 285, 24.
	(c) Su, T. A.; Li, H.; Klausen, R. S.; Kim, N. T.; Neupane, M.; Leighton, J. L.; Steigerwald, M. L. Venkataraman, L.; Nuckolls, C. Acc. Chem. Res. 2017, 50, 1088.
[4]	(a) Yang, W.; Gao, X.; Wang, B. Med. Res. Rev. 2003, 23, 346.
	(b) Burkhardt, E. R.; Matos, K. Chem. Rev. 2006, 106, 2617.
[5]	Bessmertnykh, A. G.; Blinov, K. A.; Grishin, Y. K.; Donskaya, N. A.; Tveritinova, E. V.; Yur'eva, N. M.; Beletskaya, I. P. J. Org. Chem. 1997, 62, 6069.
[6]	Itazaki, M.; Nishihara, Y.; Osakada, K. J. Org. Chem. 2002, 67, 6889.
[7]	Xu, X.-M.; Gao, A.-L.; Xu, X.-F.; Li, J.-F.; Cui, C.-M. J. Am. Chem. Soc. 2024, 146, 4060.
[8]	Wu, L.; Zhang, L.; Guo, J.; Gao, J.; Ding, Y.; Ke, J.; He, C. Angew. Chem., Int. Ed. 2024, 63, e202413753.
[9]	Fu, B.; Wang, L.-H.; Chen, K.-X.; Yuan, X.-P.; Yin, J.-J.; Wang, S.-M.; Shi, D.-Z.; Zhu, B.; Guan, W.; Zhang, Q.; Xiong, T. Angew. Chem., Int. Ed. 2024, 136, e202407391.
[10]	Xiao, Z.-Y.; Wang, Z.-L.; Xu, Y.-H. Chin. J. Chem. 2025, 43, 385.
[11]	Xie, W.; Zhai, D.; Li, X.-X.; Deng, W.; Yu, S. Chem. Commun. 2025, 61, 5958.
[12]	Zhang, J.; Guo, J.; Liu, W.; Liu, M.; Zhao, D. ACS Catal. 2025, 15, 3216.
[13]	Ishiyama, T.; Momota, S.; Miyaura, N. Synlett 1999, 11, 1790.
[14]	Wang, W.-F.; Lu, K.; Liu, P.-R.; Zeng, H.-H.; Yang, L.-M.; Ma, A.-J.; Tu, Y.-Q.; Peng, J.-B. ACS Catal. 2024, 14, 5156.
[15]	Tan, B. B.; Hu, M.; Ge, S. Angew. Chem., Int. Ed. 2023, 62, e202307176.
[16]	Yu, X.; Zheng, H.; Zhao, H.; Lee, B. C.; Koh, M. J. Angew. Chem., Int. Ed. 2021, 60, 2104.
[17]	Zheng, W.; Tan, B. B.; Ge, S.; Lu, Y. J. Am. Chem. Soc. 2024, 146, 5366.
[18]	Chen, S.; Lin, J.; Song, Q. ACS Catal. 2025, 15, 13003.
[19]	Jiang, H.-C.; Tang, X.-Y.; Shi, M. Chem. Commun. 2016, 52, 5273.
[20]	Zhu, Y.-S.; Guo, Y.-L.; Zhu, Y.-Y.; Su, B. J. Am. Chem. Soc. 2024, 146, 32283.
[21]	Yuan, Y.; Ge, F.; Yang, T.; Wu, X.-F. J. Catal. 2025, 450, 116280.
[22]	Yang, L.-M.; Zeng, H.-H.; Liu, X.-L.; Ma, A.-J.; Peng, J.-B. Chem. Sci. 2022, 13, 7304.
[23]	Mondal, P. P.; Nair, A. V.; Sasidaran, M.; Chungath, A. A.; Suman, S. P.; Kuniyil, R.; Sahoo, B. Org. Lett. 2024, 26, 1458.
[24]	Tan, B. B.; Ge, S. Angew. Chem., Int. Ed. 2025, 64, e202419522.