Mechanistic Study of Palladium-Catalyzed Ring-Opening/Cross-Coupling Reactions of Silacycles

doi:10.6023/cjoc202501003

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2938-2944.DOI: 10.6023/cjoc202501003 Previous Articles Next Articles

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钯催化硅环开环/交叉偶联反应机理研究

李金霞^a^,^*(), 邓远程^a, 李嘉瑜^a, 郭益豪^a, 王广凤^a, 段阿冰^c^,^*(), 瞿双林^b^,^*()

^a 长治医学院药学院药物分子设计与新制剂长治市重点实验室山西长治 046100
^b 湖南大学化学化工学院长沙 410082
^c 湖南大学环境科学与工程学院长沙 410082

收稿日期:2025-01-04 修回日期:2025-03-12 发布日期:2025-03-31
基金资助:
湖南省青年人才(2021RC3053); 湖南省青年人才(2024RC3077); 上海市手性药物分子工程重点实验室(SMECD2024003); 长沙市自然科学基金(kq2402056); 山西省高等学校科技创新计划(2024L284); 及长治医学院博士科研启动基金(2024BS02)

Mechanistic Study of Palladium-Catalyzed Ring-Opening/Cross-Coupling Reactions of Silacycles

Jinxia Li^a^,^*(), Yuancheng Deng^a, Jiayu Li^a, Yihao Guo^a, Guangfeng Wang^a, Abing Duan^c^,^*(), Shuanglin Qu^b^,^*()

^a Changzhi Key Laboratory of Drug Molecular Design and Innovative Pharmaceutics, School of Pharmacy, Changzhi Medical College, Changzhi, Shanxi 046000
^b College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082
^c College of Environmental Science and Engineering, Hunan University, Changsha 410082

Received:2025-01-04 Revised:2025-03-12 Published:2025-03-31
Contact: *E-mail:squ@hnu.edu.cn;duanabing@hnu.edu.cn;lijinxia@hnu.edu.cn
Supported by:
Hunan Youth Talent(2021RC3053); Hunan Youth Talent(2024RC3077); Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs(SMECD2024003); Natural Science Foundation of Changsha City(kq2402056); Science and Technology Innovation Project of Shanxi Province(2024L284); Doctoral Startup Foundation of Changzhi Medical College(2024BS02)

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Abstract

Density functional theory (DFT) calculations are employed to investigate the mechanism of the Pd-catalyzed ring-opening/cross-coupling reactions of silacyclobutane and silacyclopentane, as well as the solvent effects. Computational results reveal that the two proposed reaction pathways have relatively high energy barriers. Consequently, an energetically reasonable pathway is suggested. Initially, the Pd(0) species undergoes C—Br bond oxidative addition, forming a Pd(II)-Br species. Following this, due to their distinct ring strains, the ring opening modes of the silacyclobutane and silacyclopentane systems are different. In the silacyclobutane system, the Pd(II)-Br species undergoes C—Si bond oxidative addition and the Si—Br bond reductive elimination, forming a seven-membered ring Pd(II) species. In contrast, in the silacyclopentane system, the Si atom coordinates with Br⁻ to form a five-coordinated silicon center, which then undergoes S_N2-type transmetalation, generating an eight-membered ring Pd(II) species. Finally, the resulting Pd(II) species undergoes C—C bond reductive elimination, Si—Br bond oxidative addition, and etherification, producing sila-tetralins and sila-benzosuberanes. A comparison of solvents with varying polarities shows that adding N,N-dimethylacetamide (DMF) increases the polarity of the silacyclopentane system and lowers the energy of the S_N2-type transmetalation, thereby facilitating the ring-opening of silacyclopentane.

Key words: silacyclobutane, silacyclopentane, cross-coupling reaction, density functional theory calculation, S_N2-type transmetalation

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Jinxia Li, Yuancheng Deng, Jiayu Li, Yihao Guo, Guangfeng Wang, Abing Duan, Shuanglin Qu. Mechanistic Study of Palladium-Catalyzed Ring-Opening/Cross-Coupling Reactions of Silacycles[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2938-2944.

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Fig. & Tab. 6

Scheme 1. Pd-catalyzed ring-opening/cross-coupling reactions of silacyclobutane and silacyclopentane

Scheme 2. General mechanism for Pd-catalyzed ring-opening/cross-coupling reactions of silacycles

Figure 1. Calculated free energy profiles for Pd-catalyzed ring-opening/cross-coupling reactions of silacyclobutane

Figure 2. Calculated free energy profiles for Pd-catalyzed ring-opening/cross-coupling reactions of silacyclopentane

Solvent	ε_r^b/(F•m^－1)	ΔG^≠/(kcal•mol^－1)		∆∆G^≠(TS8A－TS3A)/(kcal•mol^－1)
Solvent	ε_r^b/(F•m^－1)	TS3A	TS8A	∆∆G^≠(TS8A－TS3A)/(kcal•mol^－1)
THF	7.4	34.2	34.4	0.2
^tBuOH	12.5	33.4	34.8	1.4
CyOH	17.0	33.3	35.3	2.0
Acetone	20.5	33.0	35.1	2.1
DMF	37.2	32.7	35.2	2.5
CyOH/DMF (V∶V=1∶1)		32.9	35.6	2.7

Table 1. Gibbs free energy of TS3A and TS8A in various solvents

Scheme 3. A refined mechanism of Pd-catalyzed ring-opening/cross-coupling reactions of silacycles

References 38

[1]	Ishida, N.; Okumura, S.; Kawasaki, T.; Murakami, M. Angew. Chem., Int. Ed. 2018, 57, 11399.
[2]	Wu, Y.; Wang, P. Angew. Chem., Int. Ed. 2022, 61, e202205382.
[3]	Wang, Q.; Jiang, H.-M.; Zhuo, S.; Xu, L.-P. Catal. Sci. Technol. 2022, 12, 135.
[4]	Rémond, E.; Martin, C.; Martinez, J.; Cavelier, F. Chem. Rev. 2016, 116, 11654.
[5]	Hailes, R. L. N.; Oliver, A. M.; Gwyther, J.; Whittell, G. R.; Manners, I. Chem. Soc. Rev. 2016, 45, 5358.
[6]	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.
[7]	Gan, W.-E.; Wu, Y.-S.; Wu, B.; Fang, C.-Y.; Cao, J.; Xu, Z.; Xu, L.-W. Angew. Chem., Int. Ed. 2024, 63, e202317973.
[8]	Wu, L.; Zhang, L.; Guo, J.; Gao, J.; Ding, Y.; Ke, J.; He, C. Angew. Chem., Int. Ed. 2024, 63, e202413753.
[9]	Cui, D.; Feng, Y.; Gan, Y.; Yin, J.; Wang, W.; Fan, Y.; Gao, L.; Ke, B.; Song, Z. Org. Chem. Front. 2022, 9, 5453.
[10]	Luo, G.; Chen, L.; Li, Y.; Fan, Y.; Wang, D.; Yang, Y.; Gao, L.; Jiang, R.; Song, Z. Org. Chem. Front. 2021, 8, 5941.
[11]	Franz, A. K.; Wilson, S. O. J. Med. Chem., 2013, 56, 388.
[12]	Ramesh, R.; Reddy, D. S. J. Med. Chem, 2017, 61, 3779.
[13]	Liu, Y.-J.; Liu, Y.-H.; Zhang, Z.-Z.; Yan, S.-Y.; Chen, K.; Shi, B.-F. Angew. Chem., Int. Ed. 2016, 55, 13859.
[14]	Wang, W.; Zhou, S.; Li, L.; He, Y.; Dong, X.; Gao, L.; Wang, Q.; Song, Z. J. Am. Chem. Soc. 2021, 143, 11141.
[15]	Kinnaird, J. W. A.; Ng, P. Y.; Kubota, K.; Wang, X.; Leighton, J. L. J. Am. Chem. Soc. 2002, 124, 7920. pmid: 12095334
[16]	Zhang, X.; Houk, K. N.; Leighton, J. L. Angew. Chem., Int. Ed. 2005, 44, 938.
[17]	Li, L.; Zhang, Y.; Gao, L.; Song, Z. Tetrahedron Lett. 2015, 56, 1466.
[18]	Zhao, W. T.; Gao, F.; Zhao, D. Angew. Chem. Int. Ed. 2018, 57, 6329.
[19]	Chen, H.; Peng, J.; Pang, Q.; Du, H.; Huang, L.; Gao, L.; Lan, Y.; Yang, C.; Song, Z. Angew. Chem., Int. Ed. 2022, 61, e202212889.
[20]	Chen, H.; Zhang, H.; Du, H.; Kuang, Y.; Pang, Q.; Wang, W.; Yang, C.; Song, Z. Org. Lett. 2023, 25, 1558.
[21]	Tang, X.; Zhang, Y.; Tang, Y.; Li, Y.; Zhou, J.; Wang, D.; Gao, L.; Su, Z.; Song, Z. ACS Catal. 2022, 12, 5185.
[22]	Zhu, W.; Xu, L. Chin. J. Org. Chem. 2023, 43, 362 (in Chinese).
	(祝炜轲, 徐利文, 有机化学, 2023, 43, 362.) doi: 10.6023/cjoc202300003
[23]	Yin, G.; Xu, L. Chin. J. Org. Chem. 2021, 41, 4839 (in Chinese).
	(尹官武, 徐利文, 有机化学, 2021, 41, 4839.) doi: 10.6023/cjoc202100094
[24]	Chen, S.; He, X.; Chen, J.; Zhang, W.; Yang, Y.; Liu, S., Lan, Y.; Houk, K. N.; Shen, X. Angew. Chem., Int. Ed. 2022, 61, e202213431.
[25]	Tang, X.; Tang, Y.; Peng, J.; Du, H.; Huang, L.; Gao, J.; Liu, S.; Wang, D.; Wang, W.; Gao, L.; Lan, Y.; Song, Z. J. Am. Chem. Soc. 2024, 146, 26639.
[26]	Huo, J.; Zhong, K.; Xue, Y.; Lyu, M. M.; Ping, Y.; Liu, Z.; Lan, Y.; Wang, J. J. Am. Chem. Soc. 2021, 143, 12968.
[27]	Qin, Y.; Han, J.-L.; Ju, C.-W.; Zhao, D. Angew. Chem., Int. Ed. 2020, 59, 8481.
[28]	Chen, W. J.; Lin, Z. Dalton Trans. 2014, 43, 11138.
[29]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision C.01, Gaussian, Inc., Wallingford CT, 2019.
[30]	Becke, A. D. Phys. Rev. A 1988, 38, 3098.
[31]	Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/physrevb.37.785 pmid: 9944570
[32]	Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
[33]	Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104.
[34]	Becke, A. D.; Johnson, E. R. J. Chem. Phys. 2005, 123, 154101.
[35]	Johnson, E. R.; Becke, A. D. J. Chem. Phys. 2006, 124, 174104.
[36]	Fukui, K. Acc. Chem. Res. 1981, 14, 363.
[37]	Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378.
[38]	Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215.

钯催化硅环开环/交叉偶联反应机理研究

Mechanistic Study of Palladium-Catalyzed Ring-Opening/Cross-Coupling Reactions of Silacycles

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