Recent Progress in Radical-Mediated Si—H Functionalization of Silanes: An Effective Strategy for the Synthesis of Organosilanes Containing C—Si Bond

doi:10.6023/cjoc202207047

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (12): 4122-4151.DOI: 10.6023/cjoc202207047 Previous Articles Next Articles

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自由基介导的硅烷Si—H键官能团化研究进展: 一种合成含C—Si键有机硅化合物的有效策略

杨惜晖^a, 高皓炜^a, 闫甲乐^a, 史雷^a^,^b^,^*()

a 哈尔滨工业大学(深圳) 广东深圳 518055
b 广东省催化化学重点实验室广东深圳 518055

收稿日期:2022-07-31 修回日期:2022-08-28 发布日期:2022-09-23
通讯作者: 史雷
作者简介:
^†共同第一作者
基金资助:
国家自然科学基金(21871067); 国家自然科学基金(22271069); 广东省自然科学基金(2021A1515010190); 元素有机化学国家重点实验室(202009); 广东省催化化学重点实验室(2020B121201002); 中央高校基本科研业务费专项资金(HIT.OCEF.2021035)

Recent Progress in Radical-Mediated Si—H Functionalization of Silanes: An Effective Strategy for the Synthesis of Organosilanes Containing C—Si Bond

Xihui Yang^a, Haowei Gao^a, Jiale Yan^a, Lei Shi^a^,^b()

a Harbin Institute of Technology (Shenzhen), Shenzhen, Guangdong 518055
b Guangdong Provincial Key Laboratory of Catalysis, Shenzhen, Guangdong 518055

Received:2022-07-31 Revised:2022-08-28 Published:2022-09-23
Contact: Lei Shi
About author:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21871067); National Natural Science Foundation of China(22271069); Natural Science Foundation of Guangdong Province(2021A1515010190); Open Project Program of State Key Laboratory of Elemento-Organic Chemistry(202009); Guangdong Provincial Key Laboratory of Catalysis(2020B121201002); Fundamental Research Funds for the Central Universities(HIT.OCEF.2021035)

Organosilanes are versatile intermediates and products in material chemistry, pharmaceutical chemistry and synthetic chemistry because of their unique physical, chemical and physiological properties. In the past century, the synthesis of organosilanes containing C—Si bonds has gradually become one of the research hotspots. Due to the high tolerance of functional groups, good atomic economy and chemoselectivity of radical chemistry, the construction of C—Si bond via free radical silylation reaction has achieved great progress in recent years. The research progress of the radical silylation reactions exploring silane as the precursor of silicon radical in the last decade is summarized, and the related reaction mechanism is discussed.

Key words: silicon radical, visible-light catalysis, organic peroxide, carbon-silicon bond

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Xihui Yang, Haowei Gao, Jiale Yan, Lei Shi. Recent Progress in Radical-Mediated Si—H Functionalization of Silanes: An Effective Strategy for the Synthesis of Organosilanes Containing C—Si Bond[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4122-4151.

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Fig. & Tab. 52

Figure 1. Advantages of introducing silicon in druglike scaffolds

Figure 2. Formation of silicon radical and BDE values of selected Si—H bond

Figure 3. Three typical reaction mechanisms for radical-mediated Si—H functionalization1

Scheme 1. Copper-catalyzed decarboxylative silylation of α,β- unsaturated acids[7]

Scheme 2. Cu-catalyzed silylation of alkenes

Scheme 3. Synthesis of alkenyl silanes via C—S bond cleavage

Scheme 4. Copper-catalyzed denitro silylation of β-nitroalkenes

Scheme 5. Metal-free dehydrogenative silylation of enamides

Scheme 6. Photocatalytic synthesis of diarylmethyl silanes

Scheme 7. Copper-catalyzed silylarylation of activated alkenes

Scheme 8. Copper-catalyzed radical silylarylation of ynones

Scheme 9. Copper-catalyzed radical 1,2-aryl migration in α,α- diaryl allylic alcohols

Scheme 10. Copper-catalyzed silylation and dearomatization of activated alkynes

Scheme 11. Iron-catalyzed silylation and dearomatization of activated alkynes

Scheme 12. Copper-catalyzed heteroarylsilylation of unactivated olefins

Scheme 13. Iron-catalyzed intermolecular 1,2-difunctionalization of styrenes

Scheme 14. Cu catalyzed silylperoxidation of α,β-unsaturated carbonyl compounds and conjugated enynes

Scheme 15. Cascade cyclization reaction to afford silyl-functionalized pyrido[2-gh]phenanthridin derivatives

Scheme 16. DTBP mediated carboxysilylation of unsaturated carboxylic acids

Scheme 17. Iron-Catalyzed Silylation and Spirocyclization of Biaryl-Ynones

Scheme 18. Copper-catalyzed cascade difunctionalization of N-allyl anilines

Scheme 19. Transition-metal-free intramolecular radical silylation of 2-diphenylsilylbiaryls

Scheme 20. Synthesis of silafluorenes and silaindenes

Scheme 21. Free-radical-promoted site-selective C—H silylation of arenes

Scheme 22. Selective C?5 radical silylation of imidazopyridines promoted by Lewis acid

Scheme 23. TBHP-promoted radical silylation and aromatisation of aryl isonitriles

Scheme 24. Copper-catalyzed synthesis of silicon-containing five- and six-membered heterocycles

Scheme 25. Photocatalyzed hydrosilylation of electron-poor alkenes

Scheme 26. Visible-light-mediated metal-free hydrosilylation of electron-poor alkenes

Scheme 27. Visible-light-mediated metal-free hydrosilylation of electron-rich alkenes

Scheme 28. Free radical hydrosilylation of electrically neutral and electron rich olefins induced by visible light

Scheme 29. Radical hydrosilylation of alkynes catalyzed by eosin Y

Scheme 33. Visible-light-driven radical hydrosilylation of allenes

Scheme 31. Manganese-catalyzed Z-selective hydrosilylation of alkynes

Scheme 32. Visible-light-mediated metal-free difunctionalization of alkenes

Scheme 33. Nickel-catalyzed arylsilylation of electron-deficient alkenes

Scheme 34. Visible-light-driven silylative cyclization of aza-1,6-dienes

Scheme 35. Visible-light mediated radical cyclizations of enynes and dienes

Scheme 36. Free-radical-promoted decarboxylative silylation of α,β-unsaturated acids

Scheme 37. Electrochemical radical silyl-oxygenation of electron-deficient alkenes

Scheme 38. Visible-light induced radical intramolecular radical silylation of biarylhydrosilanes

Scheme 39. Photocatalytic C—H silylation of heteroarenes

Scheme 40. Photochemical silylation of pyridines

Scheme 41. Organic photoredox catalyzed C—H silylation of quinoxalinones or electron-deficient heteroarenes

Scheme 42. Photoinduced silylation of N-heteroarenes and unsaturated benzamides

Scheme 43. Dehydrosilylation of alkenes by photoredox, hydrogen-atom tansfer, and cobalt catalysis

Scheme 44. Light-mediated defluorosilylation of α-trifluoromethyl arylalkenes

Scheme 45. Photoredox metal-free allylic defluorinative silylation of α?trifluoromethylstyrenes

Scheme 46. Photocatalytic synthesis of diarylmethyl silanes

Scheme 47. Trans-Selective Radical Silylzincation of Ynamides

Scheme 48. Potassium tert-butoxide-catalyzed silylation of C—H bonds in aromatic heterocycles

Scheme 49. Manganese-catalyzed dehydrosilylation and hydrosilylation of alkenes

References 58

[1]	Du, X.; Huang, Z. ACS Catal. 2017, 7, 1227. doi: 10.1021/acscatal.6b02990
[2]	Ramesh, R.; Reddy, D. S. J. Med. Chem. 2018, 61, 3779. doi: 10.1021/acs.jmedchem.7b00718 pmid: 29039662
[3]	(a) Brook, M. A. Silicon in Organic, Organometallic, and Polymer Chemistry, Wiley, New York, 2000.
	(b) Bähr, S.; Xue, W.; Oestreich, M. ACS Catal. 2018, 9, 16-24. doi: 10.1021/acscatal.8b04230
[4]	Parsaee, F.; Senarathna, M. C.; Kannangara, P. B.; Alexander, S. N.; Arche, P. D. E.; Welin, E. R. Nat. Rev. Chem. 2021, 5, 486. doi: 10.1038/s41570-021-00284-3
[5]	Lu, L.; Siu, J. C.; Lai, Y.; Lin, S. J. Am. Chem. Soc. 2020, 142, 21272. doi: 10.1021/jacs.0c10899
[6]	(a) Vulovic, B.; Cinderella, A. P.; Watson, D. A. ACS Catal. 2017, 7, 8113. doi: 10.1021/acscatal.7b03465 pmid: 29868244
	(b) Lalonde, M.; Chan, T. H. Synthesis 1985, 817. pmid: 29868244
[7]	(a) Shang, X.; Liu, Z.-Q. Org. Biomol. Chem. 2016, 14, 7829. doi: 10.1039/C6OB00797J pmid: 29938502
	(b) Zhang, X. P.; Fang, J. K.; Cai, C.; Lu, G. P. Chin. Chem. Lett. 2021, 32, 1280. doi: 10.1016/j.cclet.2020.09.058 pmid: 29938502
	(c) Li, J.-S.; Wu, J. ChemPhotoChem 2018, 2, 839. doi: 10.1002/cptc.201800110 pmid: 29938502
	(d) Chatgilialoglu, C.; Ferreri, C.; Landais, Y.; Timokhin, V. I. Chem. Rev. 2018, 118, 6516. doi: 10.1021/acs.chemrev.8b00109 pmid: 29938502
[8]	Zhang, L.; Hang, Z.; Liu, Z. Q. Angew. Chem., Int. Ed. 2016, 55, 236. doi: 10.1002/anie.201509537
[9]	Gu, J.; Cai, C. Chem. Commun. 2016, 52, 10779. doi: 10.1039/C6CC05509E
[10]	Xu, R.; Cai, C. Catal. Commun. 2018, 107, 5. doi: 10.1016/j.catcom.2017.12.023
[11]	Lin, Y. M.; Lu, G. P.; Wang, R. K.; Yi, W. B. Org. Lett. 2017, 19, 1100. doi: 10.1021/acs.orglett.7b00126
[12]	Zhang, X.; Liu, M.-X.; Wang, T.-L.; Wang, Y.-Q.; Wang, X.-C.; Quan, Z.-J. Org. Chem. Front. 2019, 6, 3365. doi: 10.1039/c9qo00819e
[13]	Chang, X. H.; Wang, Z. L.; Zhao, M.; Yang, C.; Li, J. J.; Ma, W. W.; Xu, Y. H. Org. Lett. 2020, 22, 1326. doi: 10.1021/acs.orglett.9b04645
[14]	Gan, Q. C.; Song, Z. Q.; Tung, C. H.; Wu, L. Z. Org. Lett. 2022, 24, 5192. doi: 10.1021/acs.orglett.2c02022
[15]	Zhang, L.; Liu, D.; Liu, Z. Q. Org. Lett. 2015, 17, 2534. doi: 10.1021/acs.orglett.5b01067
[16]	Yan, Z.; Xie, J.; Zhu, C. Adv. Synth. Catal. 2017, 359, 4153. doi: 10.1002/adsc.201700926
[17]	Peng, H.; Yu, J. T.; Jiang, Y.; Cheng, J. Org. Biomol. Chem. 2015, 13, 10299. doi: 10.1039/C5OB01855B
[18]	Gao, P.; Zhang, W.; Zhang, Z. Org. Lett. 2016, 18, 5820. doi: 10.1021/acs.orglett.6b02781
[19]	Wu, L.-J.; Tan, F.-L.; Li, M.; Song, R.-J.; Li, J.-H. Org. Chem. Front. 2017, 4, 350. doi: 10.1039/C6QO00691D
[20]	Zhang, H.; Wu, X.; Zhao, Q.; Zhu, C. Chem. Asian J. 2018, 13, 2453. doi: 10.1002/asia.201800150
[21]	Yang, Y.; Song, R. J.; Ouyang, X. H.; Wang, C. Y.; Li, J. H.; Luo, S. Angew. Chem., Int. Ed. 2017, 56, 7916. doi: 10.1002/anie.201702349
[22]	Lan, Y.; Chang, X.-H.; Fan, P.; Shan, C.-C.; Liu, Z.-B.; Loh, T.-P.; Xu, Y.-H. ACS Catal. 2017, 7, 7120. doi: 10.1021/acscatal.7b02754
[23]	Zhang, C.; Pi, J.; Wang, L.; Liu, P.; Sun, P. Org. Biomol. Chem., 2018, 16, 9223. doi: 10.1039/c8ob02670j pmid: 30475364
[24]	Nozawa-Kumada, K.; Ojima, T.; Inagi, M.; Shigeno, M.; Kondo, Y. Org. Lett. 2020, 22, 9591. doi: 10.1021/acs.orglett.0c03640 pmid: 33269934
[25]	Chen, F.; Zheng, Y.; Yang, H.; Yang, Q. Y.; Wu, L. Y.; Zhou, N. Adv. Synth. Catal. 2022, 364, 1537. doi: 10.1002/adsc.202200049
[26]	Xue, Y.; Guo, Z.; Chen, X.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Org. Biomol. Chem. 2022, 20, 989. doi: 10.1039/D1OB02318G
[27]	Leifert, D.; Studer, A. Org. Lett. 2015, 17, 386. doi: 10.1021/ol503574k pmid: 25536028
[28]	Xu, Z.; Chai, L.; Liu, Z. Q. Org. Lett. 2017, 19, 5573. doi: 10.1021/acs.orglett.7b02717
[29]	Li, Y.; Shu, K.; Liu, P.; Sun, P. Org. Lett. 2020, 22, 6304. doi: 10.1021/acs.orglett.0c02131
[30]	Wang, L.; Zhu, H.; Guo, S.; Cheng, J.; Yu, J. T. Chem. Commun. 2014, 50, 10864. doi: 10.1039/C4CC04773G
[31]	Yang, Y.; Song, R. J.; Li, Y.; Ouyang, X. H.; Li, J. H.; He, D. L. Chem. Commun. 2018, 54, 1441. doi: 10.1039/C7CC08964C
[32]	Qrareya, H.; Dondi, D.; Ravelli, D.; Fagnoni, M. ChemCatChem 2015, 7, 3350. doi: 10.1002/cctc.201500562
[33]	Zhou, R.; Goh, Y. Y.; Liu, H.; Tao, H.; Li, L.; Wu, J. Angew. Chem., Int. Ed. 2017, 56, 16621. doi: 10.1002/anie.201711250
[34]	Zhu, J.; Cui, W.-C.; Wang, S.; Yao, Z.-J. J. Org. Chem. 2018, 83, 14600. doi: 10.1021/acs.joc.8b02409
[35]	Zhu, J.; Cui, W. C.; Wang, S.; Yao, Z. J. Org. Lett. 2018, 20, 3174. doi: 10.1021/acs.orglett.8b00909
[36]	Cai, Y.; Zhao, W.; Wang, S.; Liang, Y.; Yao, Z. J. Org. Lett. 2019, 21, 9836. doi: 10.1021/acs.orglett.9b03679
[37]	Liang, H.; Ji, Y. X.; Wang, R. H.; Zhang, Z. H.; Zhang, B. Org. Lett. 2019, 21, 2750. doi: 10.1021/acs.orglett.9b00701 pmid: 30931573
[38]	Hou, J.; Ee, A.; Cao, H.; Ong, H. W.; Xu, J. H.; Wu, J. Angew. Chem., Int. Ed. 2018, 57, 17220. doi: 10.1002/anie.201811266
[39]	Zhang, Z.; Hu, X. ACS Catal. 2019, 10, 777. doi: 10.1021/acscatal.9b04916
[40]	Cui, W. C.; Zhao, W.; Gao, M.; Liu, W.; Wang, S.; Liang, Y.; Yao, Z. J. Chem.-Eur. J. 2019, 25, 16506. doi: 10.1002/chem.201903440
[41]	Hou, H.; Xu, Y.; Yang, H.; Chen, X.; Yan, C.; Shi, Y.; Zhu, S. Org. Lett. 2020, 22, 1748. doi: 10.1021/acs.orglett.0c00024
[42]	Neogi, S.; Kumar Ghosh, A.; Mandal, S.; Ghosh, D.; Ghosh, S.; Hajra, A. Org. Lett. 2021, 23, 6510. doi: 10.1021/acs.orglett.1c02322
[43]	Ke, J.; Liu, W.; Zhu, X.; Tan, X.; He, C. Angew. Chem., Int. Ed. 2021, 60, 8744. doi: 10.1002/anie.202016620
[44]	Yang, C.; Wang, J.; Li, J.; Ma, W.; An, K.; He, W.; Jiang, C. Adv. Synth. Catal. 2018, 360, 3049. doi: 10.1002/adsc.201800417
[45]	Liu, S.; Pan, P.; Fan, H.; Li, H.; Wang, W.; Zhang, Y. Chem. Sci. 2019, 10, 3817. doi: 10.1039/C9SC00046A
[46]	Rammal, F.; Gao, D.; Boujnah, S.; Hussein, A. A.; Lalevée, J.; Gaumont, A.-C.; Morlet-Savary, F.; Lakhdar, S. ACS Catal. 2020, 10, 13710. doi: 10.1021/acscatal.0c03726
[47]	Dai, C.; Zhan, Y.; Liu, P.; Sun, P. Green Chem. 2021, 23, 314. doi: 10.1039/D0GC03697H
[48]	Zhang, W.; Lu, Q.; Wang, M.; Zhang, Y.; Xia, X. F.; Wang, D. Org. Lett. 2022, 24, 3797. doi: 10.1021/acs.orglett.2c01330
[49]	Yu, W. L.; Luo, Y. C.; Yan, L.; Liu, D.; Wang, Z. Y.; Xu, P. F. Angew. Chem., Int. Ed. 2019, 58, 10941 doi: 10.1002/anie.201904707
[50]	Inoue, M.; Sumii, Y.; Shibata, N. ACS Omega 2020, 5, 10633. doi: 10.1021/acsomega.0c00830
[51]	Yue, F.; Liu, J.; Ma, H.; Liu, Y.; Dong, J.; Wang, Q. Org. Lett. 2022, 24, 4019. doi: 10.1021/acs.orglett.2c01448
[52]	Luo, C.; Zhou, Y.; Chen, H.; Wang, T.; Zhang, Z. B.; Han, P.; Jing, L. H. Org. Lett. 2022, 24, 4286. doi: 10.1021/acs.orglett.2c01690
[53]	Luo, C.; Lu, W. H.; Wang, G. Q.; Zhang, Z. B.; Li, H. Q.; Han, P.; Yang, D.; Jing, L. H.; Wang, C. J. Org. Chem. 2022, 87, 3567. doi: 10.1021/acs.joc.1c03125
[54]	Romain, E.; Fopp, C.; Chemla, F.; Ferreira, F.; Jackowski, O.; Oestreich, M.; Perez-Luna, A. Angew. Chem., Int. Ed. 2014, 53, 11333. doi: 10.1002/anie.201407002
[55]	Toutov, A. A.; Liu, W. B.; Betz, K. N.; Fedorov, A.; Stoltz, B. M.; Grubbs, R. H. Nature 2015, 518, 80. doi: 10.1038/nature14126
[56]	Liu, W. B.; Schuman, D. P.; Yang, Y. F.; Toutov, A. A.; Liang, Y.; Klare, H. F. T.; Nesnas, N.; Oestreich, M.; Blackmond, D. G.; Virgil, S. C.; Banerjee, S.; Zare, R. N.; Grubbs, R. H.; Houk, K. N.; Stoltz, B. M. J. Am. Chem. Soc. 2017, 139, 6867. doi: 10.1021/jacs.6b13031
[57]	Dong, J.; Yuan, X. A.; Yan, Z.; Mu, L.; Ma, J.; Zhu, C.; Xie, J. Nat. Chem. 2021, 13, 182. doi: 10.1038/s41557-020-00589-8 pmid: 33318674
[58]	Walsh, R. Acc. Chem. Res. 1981, 14, 246. doi: 10.1021/ar00068a004

自由基介导的硅烷Si—H键官能团化研究进展: 一种合成含C—Si键有机硅化合物的有效策略

Recent Progress in Radical-Mediated Si—H Functionalization of Silanes: An Effective Strategy for the Synthesis of Organosilanes Containing C—Si Bond

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