Research Progress on Transition Metal-Catalyzed Carbosilylation of Alkenes

doi:10.6023/cjoc202507033

Abstract

As functional molecules, organosilicon compounds have important applications in the fields of organic synthesis, materials science and drug development. Carbosilylation of alkenes is a key reaction for synthesizing structurally rich organosilicon compounds and has important applications in constructing structurally diverse organosilicon compounds. The research progress of alkene carbosilylation with different electrophile reagents is systematically reviewed, the basic principle is described in detail, the advantages and limitations of each catalytic system are analyzed, and the future development direction of alkene siliconization reaction is prospected.

Key words: transition metal, alkenes, carbosilylation

Cite this article

Meng Liu, Taobo Liu, Meilan Han, Shuyang Wang, Zhipaicuo Gui, Guangli Xu, Hongping Han. Research Progress on Transition Metal-Catalyzed Carbosilylation of Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 840-858.

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Fig. & Tab. 23

Figure 1. Drug molecules containing silicon

Scheme 1. Palladium-catalyzed aromatic silicification of diene and its mechanism

Scheme 2. Palladium-catalyzed arylsilylation of inactive alkenes

Scheme 3. Nickel and copper bimetallic catalytic alkenes arylsilylation reaction and its mechanism

Scheme 4. Iron/ruthenium bimetallic catalyzed hydroarylsilylation of alkenes

Scheme 5. Nickel-catalyzed 1,3-conjugated diene arylsilyl reaction and its mechanism

Scheme 6. Copper-catalyzed alkenes arylsilylation reaction and its mechanism

Scheme 7. Copper-catalyzed alkenes arylsilylation reaction and its mechanism

Scheme 8. Alkali-catalyzed alkenes arylsilylation reaction and its mechanism

Scheme 9. Organic base catalyzed alkenes arylsilylation reaction

Scheme 10. Photo-promoted nickel-catalyzed alkenes arylsilylation reactionand its mechanism

Scheme 11. Photocatalytic alkenes arylsilylation reaction

Scheme 12. Palladium-catalyzed 1,3-conjugated diene silanization reaction

Scheme 13. Titanium-catalyzed silanization of alkenes

Scheme 14. Nickel catalyzed silanization of 1,3-conjugated diene

Scheme 15. Nickel-catalyzed silanization of acrylonitrile

Scheme 16. Nickel catalyzed silanization of inactive alkenes

Scheme 17. Copper-catalyzed silicylation and carboxylation reactions of alkenes

Scheme 18. Photocatalytic silicylation and carboxylation reactions of alkenes

Scheme 19. Nickel-catalyzed silicification and acylation of alkenes

Scheme 20. Photoelectrochemically promoted iron/nickel co-catalyzed hydrosilylation of alkenes

Scheme 21. Palladium-catalyzed siliconization and acylation of diene

Scheme 22. Organic cation-catalyzed alkenyne silylation reaction

References 47

[1]	(a) Denmark, S. E.; Sweis, R. F. Acc. Chem. Res. 2002, 35, 835.
	(b) Pozdnyakov, A.; Kuznetsova, N.; Ivanova, A.; Bolgova, Y.; Semenova, T.; Trofimova, O.; Prozorova, G.; Emel'yanov, A. Mater. Today Chem. 2023, 34, 101808.
	(c) Wang, Z.-L.; Zhu, R. J. Am. Chem. Soc. 2024, 146, 19377.
	(d) Yamashita, D.; Fang, N.; Fujii, S.; Kato, K. Y. Adv. Opt. Mater. 2025, 13, 2402531.
	(e) Chen, K.; Wu, X.; Yao, J.; Liao, H.; Ran, Q. Chem. Eng. J. 2025, 518, 164613.
[2]	(a) Franz, A. K.; Wilson, S. O. J. Med. Chem. 2013, 56, 388.
	( (b) Ye, T. T.; Wang, Q. Y.; Shen, L. H.; Cao, D.; Wu, H. L.; Yin, X. P. J. Hangzhou Norm. Univ. (Nat. Sci.) 2013, 12, 555 (in Chinese).
	(叶婷婷, 王秋岩, 沈凌宏, 曹丹, 吴慧丽, 殷晓浦, 杭州师范大学学报(自然科学版), 2013, 12, 555.)
	(c) Fujii, S.; Hashimoto, Y. Future Med. Chem. 2017, 9, 485.
	(d) Panayides, J.-L.; Riley, D. L.; Hasenmaile, F.; van Otterlo, W. A. L. RSC Med. Chem. 2024, 15, 3286.
[3]	(a) Matsumoto, K.; Huang, J.; Naganawa, Y.; Guo, H.; Beppu, T.; Sato, K.; Shimada, S.; Nakajima, Y. Org. Lett. 2018, 20, 2481.
	(b) Pang, X.; Shu, X.-Z. Chem.-Eur. J. 2023, 29, e202203362.
	(c) Zhang, Y.-F.; Li, L.; Tang, Y.; Zhou, Y.-Y. Org. Lett. 2025, 27, 4032.
[4]	(a) Tobisu, M.; Kita, Y.; Ano, Y.; Chatani, N. J. Am. Chem. Soc. 2008, 130, 15982.
	(b) Chu, C. K.; Liang, Y.; Fu, G. C. J. Am. Chem. Soc. 2016, 138, 6404.
	(c) Xue, W.; Oestreich, M. Angew. Chem., Int. Ed. 2017, 56, 11649.
	(d) Xue, W.; Shishido, R.; Oestreich, M. Angew. Chem., Int. Ed. 2018, 57, 12141.
[5]	(a) Yamamoto, E.; Ukigai, S.; Ito, H. Synlett 2017, 28, 2460.
	(b) Cai, Y.; Zhao, W.; Wang, S.; Liang, Y.; Yao, Z.-J. Org. Lett. 2019, 21, 9836.
	(c) Denker, L.; Wullschläger, D.; Martínez, J. P.; Świerczewski, S.; Trzaskowski, B.; Tamm, M.; Frank, R. ACS Catal. 2023, 13, 2586.
	(d) Li, Z.; Liu, J.-G.; Zhang, W.-P.; Xu, M.-H. Adv. Synth. Catal. 2024, 366, 2514.
	(e) Chen, S.-H.; Zhang, S.; Chen, Z.-Y.; Wu, Y.; Wang, P. J. Am. Chem. Soc. 2025, 147, 15666.
[6]	(a) Guseva, M. A.; Alentiev, D. A.; Bermesheva, E. V.; Zamilatskov, I. A.; Bermeshev, M. V. RSC Adv. 2019, 9, 33029.
	(b) Hu, M.-Y.; He, P.; Qiao, T.-J.; Sun, W.; Li, W.-T.; Lian, J.; Li, J.-H.; Zhu, S.-F. J. Am. Chem. Soc. 2020, 142, 16894.
	(c) Wei, D.; Buhaibeh, Y.; Canac, Y.; Sortais, J.-B. Molecules 2021, 26, 2598.
	(d) Zhang, S.; Findlater, M. ACS Catal. 2023, 13, 8731.
	( (e) Yang, C.; Chen, J.; Li, X.; Meng, L.; Wang, K.; Sun, W.; Fan, B. Acta Chim. Sinica 2023, 81, 1 (in Chinese).
	(杨春晖, 陈景超, 李新汉, 孟丽, 王凯民, 孙蔚青, 樊保敏, 化学学报, 2023, 81, 1.)
	(f) Coschigano, M. G.; Gregory, S. L.; Catazaro, J.; Rossini, A. J.; Klausen, R. S. Macromolecules 2024, 57, 4095.
[7]	(a) Zhang, L.; An, K.; Wang, Y.; Wu, Y.-D.; Zhang, X.; Yu, Z.-X.; He, W. J. Am. Chem. Soc. 2021, 143, 3571.
	(b) Kong, Y.; Mu, D. Chem. - Asian J. 2022, 71, e202200104.
	(c) Empel, C.; Jana, S.; Langletz, T.; Koenigs, R. M. Chem.-Eur. J. 2022, 28, e202104321.
	(d) Thorwart, T.; Greb, L. Chem. Sci. 2023, 14, 11237.
	( (e) Deng, S.; Peng, C.; Niu, Y.; Xu, Y.; Zhang, Y.; Chen, X.; Wang, H.; Liu, S.; Shen, X. Acta Chim. Sinica 2024, 82, 119 (in Chinese).
	(邓沈娜, 彭常春, 牛云宏, 许云, 张云霄, 陈祥, 王红敏, 刘珊珊, 沈晓, 化学学报, 2024, 82, 119.)
[8]	(a) You, Q.; Zhang, J.; Zhou, X. Chem.-Eur. J. 2020, 34, 7702.
	(b) You, L.; Yuan, W.; He, C. Eur. J. Org. Chem. 2021, 3079.
	(c) Ge, Y.; Ke, J.; He, C. Acc. Chem. Res. 2025, 58, 375.
[9]	(a) Hsieh, S.-Y.; Bode, J. W. Org. Lett. 2016, 18, 2098.
	(b) Yang, X.; Wang, X. Chem.-Asian. J. 2018, 13, 2307.
	(c) Yepes, P.; Suárez-Sobrino, Á. L.; Rodríguez, M. A.; Ballesteros, A. Org. Lett. 2023, 25, 1020.
	(d) Zhang, X.; Lu, K.; Chen, X.; Su, G.; Rong, X.; Ma, M. Org. Biomol. Chem. 2024, 22, 5353.
	(e) Hansjacob, P.; Schwoerer, C.; Leroux, F. R.; Donnard, M. Org. Biomol. Chem. 2024, 22, 70.
[10]	Motokura, K.; Baba, T. Green Chem. 2012, 14, 565.
[11]	Shang, X.; Liu, Z.-Q. Org. Biomol. Chem. 2016, 14, 7829.
[12]	Wang, M.; Yu, M.; Wang, W.; Lin, W.; Luo, F. Chin. J. Org. Chem. 2019, 39, 3145 (in Chinese).
	(王明凤, 余茂栋, 王文蜀, 林伟立, 罗斐贤, 有机化学, 2019, 39, 3145.)
[13]	Ghosh, S.; Lai, D.; Hajra, A. Org. Biomol. Chem. 2021, 19, 2399.
[14]	Pal, P. P.; Ghosh, S.; Hajra, A. Org. Biomol. Chem. 2023, 21, 2272.
[15]	Wu, M.-Y.; Yang, F.-Y.; Cheng, C.-H. J. Org. Chem. 1999, 64, 2471.
[16]	Liu, Z.; Chen, J.; Lu, H.-X.; Li, X.; Gao, Y.; Coombs, J. R.; Goldfogel, M. J.; Engle, K. M. Angew. Chem., Int. Ed. 2019, 58, 2.
[17]	(a) Ackerman, L. K. G.; Lovell, M. M.; Weix, D. J. Nature 2015, 524, 454.
	(b) Vázquez-Galiñanes, N.; Fañanás-Mastral, M. ChemCatChem 2018, 10, 4817.
	(c) Olivares, A. M.; Weix, D. J. J. Am. Chem. Soc. 2018, 140, 2446.
	(d) Xu, W.-Y.; Li, Y.-J.; Gong, T.-J.; Fu, Y. Org. Lett. 2022, 24, 5884.
	(e) Navrátil, R.; Kellovská K.; Baszczyňski, O. Green Chem. 2023, 25, 9779.
	(f) Serrano-Díez, E.; Pita-Milleiro, A.; Rangel-García, J.; Moreno, J. J.; Roselló-Merino, M.; Campos, J. J. Am. Chem. Soc. 2025, 147, 1271.
[18]	Zhao, B.; Li, Y.; Li, H.; Belal, M.; Zhu, L.; Yin, G. Sci. Bull. 2021, 66, 570.
[19]	Neogi, S.; Bhunya, S.; Ghosh, A. K.; Sarkar, B.; Roy, L.; Hajra, A. ACS Catal. 2024, 14, 4510.
[20]	(a) Huang, Q.; Hu, M.-Y.; Zhu, S.-F. Org. Lett. 2019, 21, 7883.
	(b) Xu, G.-L.; Liu, C.-Y.; Pang, X.; Liu, X.-Y.; Shu, X.-Z. CCS Chem. 2021, 3, 1147.
	(c) Cook, A.; St. Onge, P.; Newman, S. G. Nat. Synth. 2023, 2, 663.
	(d) Chen, R.; Intermaggio, N. E.; Xie, J.; Rossi-Ashton, J. A.; Gould, C. A.; Martin, R. T.; Alcázar, J.; MacMillan, D. W. C. Science 2024, 383, 1350.
	(e) Qi, L.; Xu, S.; Pang, X.; Wu, Y.-K.; Wang, X.; Shu, X.-Z. Angew. Chem., Int. Ed. 2025, e202509961.
[21]	Pan, Q.-Q.; Qi, L.; Pang, X.; Shu, X.-Z. Angew. Chem., Int. Ed. 2023, 62, e202215703.
[22]	Zhang, L.; Liu, D.; Liu, Z.-Q. Org. Lett. 2015, 17, 2534.
[23]	Peng, H.; Yu, J.-T.; Jiang, Y.; Cheng, J. Org. Biomol. Chem. 2015, 13, 10299.
[24]	Zhou, J.; Jiang, B.; Fujihira, Y.; Zhao, Z.; Imai, T.; Shibata, N. Nat. Commun. 2021, 12, 3749.
[25]	Cui, B.; Jia, S.; Tokunaga, E.; Shibata, N. Nat. Commun. 2018, 9, 4393.
[26]	(a) Jiao, L.; Zhou, F.-Y. Synlett 2021, 32, 159.
	(b) Xu, P.; Wang, Z.; Guo, S.-M.; Studer, A. Nat. Commun. 2024, 4121.
	(c) Bouchard, J. L.; Chang, S.; Krishnan, S.; Presley, C. C.; Boutaud, O.; Schley, N. D.; Engers, D. W.; Engers, J. L.; Lindsley, C. W.; Bender, A. M. J. Nat. Prod. 2025, 88, 996.
	(d) Hart, M. A.; Uhlenbruck, B. J. H.; Levy, J. N.; McNally, A. J. Am. Chem. Soc. 2025, 147, 18406.
[27]	(a) Hara, F. O.; Blackmond, D. G.; Baran, P. S. J. Am. Chem. Soc. 2013, 135, 12122.
	(b) Cuthberson, J. D.; MacMillan, D. W. C. Nature 2015, 519, 74.
	(c) Koniarczyk, J. L.; Greenwood, J. W.; Alegre-Requena, J. V.; Paton, R. S.; McNally, A. Angew. Chem., Int. Ed. 2019, 58, 14882.
	(d) Lee, W.; Jung, S.; Kim, M.; Hong, S. J. Am. Chem. Soc. 2021, 143, 3003.
	(e) Choi, J.; Laudadio, G.; Godineau, E.; Baran, P. S. J. Am. Chem. Soc. 2021, 143, 11927.
[28]	Gao, L.; Liu, X.; Li, G.; Chen, S.; Cao, J.; Wang, G.; Li, S. Org. Lett. 2022, 24, 5698.
[29]	(a) Blackwell, J. H.; Harris, G. R.; Smith, M. A.; Gaunt, M. J. J. Am. Chem. Soc. 2021, 143, 15946.
	(b) Zhang, H.; Chen, J.-X.; Qu, J.-P.; Kang, Y.-B. Nature 2024, 635, 610.
[30]	Zhang, Z.; Hu, X. ACS Catal. 2020, 10, 777.
[31]	Neogi, S.; Ghosh, A. K.; Mandal, S.; Ghosh, D.; Ghosh, S.; Hajra, A. Org. Lett. 2021, 23, 6510.
[32]	Zheng, W.; Xu, Y.; Luo, H.; Feng, Y.; Zhang, J.; Lin, L. Org. Lett. 2022, 24, 7145.
[33]	(a) Álvarez, R.; Vaz, B.; Gronemeyer, H.; de Lera, Á. R. Chem. Rev. 2014, 114, 1.
	(b) Zweig, J. E.; Kim, D. E.; Newhouse, T. R. Chem. Rev. 2017, 117, 11680.
[34]	(a) Huang, E.; Bunel, E.; Faul, M. F. Org. Lett. 2007, 9, 4343.
	(b) Grigalunas, M.; Ankner, T.; Norrby, P.-O.; Wiest, O.; Helquist, P. Org. Lett. 2014, 16, 3970.
[35]	Obora, Y.; Tsuji, Y.; Kawamura, T. J. Am. Chem. Soc. 1993, 115, 10414.
[36]	Nii, S.; Terao, J.; Kambe, N. J. Org. Chem. 2000, 65, 5291.
[37]	Jiang, S.; Zhang, T.; Luo, X.-Y.; Dong, S.; Ma, J.-T.; Xiao, L.-J. Angew. Chem., Int. Ed. 2025, 64, e202504494.
[38]	Sun, J.; Zhou, Y.; Gu, R.; Li, X.; Liu, A.; Zhang, X. Nat. Commun. 2022, 13, 7093.
[39]	Wang, J.; Duan, Z.; Liu, X.; Dong, S.; Chen, K.; Li, J. Angew. Chem., Int. Ed. 2022, e202202379.
[40]	Tani, Y.; Fujihara, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2014, 136, 17706.
[41]	Han, S.-M.; Wang, X.; Miao, S.; Yuab, Z.-Y.; Liu, T. RSC Adv. 2017, 7, 29035.
[42]	Hou, J.; Ee, A.; Cao, H.; Ong, H.-W.; Xu, J.-H.; Wu, J. Angew. Chem., Int. Ed. 2018, 57, 17220.
[43]	Liu, L.; Liu, W.; Cui, D.-M.; Zeng, M. Chin. J. Org. Chem. 2021, 41, 4289 (in Chinese).
	(刘亮, 刘文波, 崔冬梅, 曾明, 有机化学, 2021, 41, 4289.)
[44]	Ni, D.; Brown, M. K. ACS Catal. 2021, 11, 1858.
[45]	Wang, L.; Huo, X.; He, X.; Ackermann, L.; Wang, D. Green Chem. 2024, 26, 8315.
[46]	Inagaki, T.; Sakurai, S.; Yamanaka, M.; Tobisu, M. Angew. Chem., Int. Ed. 2022, 61, e202202387.
[47]	He, T.; Qu, Z.-W.; Klare, H. F. T.; Grimme, S.; Oestreich, M. Angew. Chem., Int. Ed. 2022, 61, e202203347.

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