Citation: Cheng Biao, Lu Peng, Zhao Jiajin, Lu Zhan. Cobalt-Catalyzed Dehydrogenative Silylation of Vinylarenes[J]. Chinese Journal of Organic Chemistry, ;2019, 39(6): 1704-1710. doi: 10.6023/cjoc201903018 shu

Cobalt-Catalyzed Dehydrogenative Silylation of Vinylarenes

Department of Chemistry, Zhejiang University, Hangzhou 310058

Corresponding author: Lu Zhan, luzhan@zju.edu.cn
Received Date: 10 March 2019
Revised Date: 3 April 2019
Available Online: 16 June 2019
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21772171), the National Basic Research Program of China (973 Program, No. 2015CB856600), the Zhejiang Provincial Natural Science Foundation (No. LR19B020001), the K. P. Chao's High Technology Development Foundation of Zhejiang University and the Fundamental Research Funds for the Central Universitiesthe National Natural Science Foundation of China 21772171the National Basic Research Program of China 2015CB856600the Zhejiang Provincial Natural Science Foundation LR19B020001

Figures(2)

A highly chemo-, regio-, and stereo-selective cobalt-catalyzed dehydrogenative silylation of vinylarenes was described. The imidazoline iminopyridine cobalt complex could promote this reaction effectively and improve the chemoselectivity dramatically. This protocol used earth-abundant transition metal, readily available alkenes and hydrosilanes to construct valuable vinylsilanes. The reaction could be carried out in gramscale and the proposed mechanism was also described.
- cobalt-catalyzed,
- dehydrogenative silylation,
- alkenes,
- vinylsilanes,
- regio-and stereo-selectivity
1. [1]
  (a) Chan, T. H.; Fleming, I. Synthesis 1979, 761.
  (b) Blumenkopf, T. A.; Overman, L. E. Chem. Rev. 1986, 86, 857.
  (c) Langkopf, E.; Schinzer, D. Chem. Rev. 1995, 95, 1375.
  (d) Fleming, I.; Barbero, A.; Water, D. Chem. Rev. 1997, 97, 2063.
2. [2]
  (a) McAtee, J. R.; Martin, S. E. S.; Ahneman, D. T.; Johnson, K. A.; Watson, D. A. Angew. Chem., Int. Ed. 2012, 51, 3663.
  (b) Martin, S. E. S.; Watson, D. A. J. Am. Chem. Soc. 2013, 135, 13330.
3. [3]
  (a) Na, Y.; Chang, S. Org. Lett. 2000, 2, 1887.
  (b) Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2001, 123, 12726.
  (c) Kawanami, Y.; Sonoda, Y.; Mori, T.; Yamamoto, K. Org. Lett. 2002, 4, 2825.
  (d) Denmark, S. E.; Pan, W. Org. Lett. 2002, 4, 4163.
  (e) Brunner, H. Angew. Chem., Int. Ed. 2004, 43, 2749.
  (f) Aricó, C. S.; Cox, L. R. Org. Biomol. Chem. 2004, 2, 2558.
  (g) Menozzi, C.; Dalko, P. I.; Cossy, J. J. Org. Chem. 2005, 70, 10717.
  (h) Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2005, 127, 17644.
  (i) Maifeld, S. V.; Tran, M. N.; Lee, D. Tetrahedron Lett. 2005, 46, 105.
  (j) Berthon-Gelloz, G.; Schumers, J.-M.; De Bo, G.; Markó, I. E. J. Org. Chem. 2008, 73, 4190.
  (k) Sore, H. F.; Blackwell, D. T.; MacDonald, S. J. F.; Spring, D. R. Org. Lett. 2010, 12, 2806.
  (l) Ding, S.-T.; Song, L.-J.; Chung, L. W.; Zhang, X.-H.; Sun, J.-W.; Wu, Y.-D. J. Am. Chem. Soc. 2013, 135, 13835.
  (m) Guo, J.; Lu, Z. Angew. Chem., Int. Ed. 2016, 55, 10835.
4. [4]
  (a) Pietraszuk, C.; Fischer, H.; Kujawa, M.; Marciniec, B. Tetrahedron Lett. 2001, 42, 1175.
  (b) Denmark, S. E.; Yang, S.-M. Org. Lett. 2001, 3, 1749.
5. [5]
  (a) Takai, K.; Kataoka, Y.; Okazoe, T.; Utimoto, K. Tetrahedron Lett. 1987, 28, 1443.
  (b) Murthi, K. K.; Salomon, R. G. Tetrahedron Lett. 1994, 35, 517.
  (c) Hodgson, D. M.; Comina, P. J. Tetrahedron Lett. 1994, 35, 9469.
  (d) Itami, K.; Nokami, T.; Yoshida, J.-I. Org. Lett. 2000, 2, 1299.
  (e) McNulty, J.; Das, P. Chem. Commun. 2008, 1244.
  (f) Mu, Q.-C.; Wang, X.-B.; Ye, F.; Sun, Y.-L.; Bai, X.-F.; Chen, J.; Xia, C.-G.; Xu, L.-W. Chem. Commun. 2018, 54, 12994.
6. [6]
  (a) Chen, C.; Hecht, M. B.; Kavara, A.; Brennessel, W. W.; Mercado, B. Q.; Weix, D. J.; Holland, P. L. J. Am. Chem. Soc. 2015, 137, 13244.
  (b) Ibrahim, A. D.; Entsminger, S. W.; Zhu, L.-Y.; Fout, A. R. ACS Catal. 2016, 6, 3589.
  (c) Jakobsson, K.; Chu, T.; Nikonov, G. I. ACS Catal. 2016, 6, 7350.
  (d) Raya, B.; Jing, S.; Balasanthiran, V.; RajanBabu, T. V. ACS Catal. 2017, 7, 2275.
  (e) Chen, Y.-J.; Ji, S.-F.; Sun, W.-M.; Chen, W.-X.; Dong, J.-C.; Wen, J.-F.; Zhang, J.; Li, Z.; Zheng, L.-R.; Chen, C.; Peng, Q.; Wang, D.-S.; Li, Y.-D. J. Am. Chem. Soc. 2018, 140, 7407.
  (f) Liu, J.-X.; Chen, W.-F.; Li, J.-F.; Cui, C.-M. ACS Catal. 2018, 8, 2230.
7. [7]
  (a) Hori, Y.; Mrrsudo, T.; Watanabe, Y. Bull. Chem. Soc. Jpn. 1988, 61, 3011.
  (b) Christ, M. L.; Sabo-Etienne, S.; Chaudret, B. Organometallics 1995, 14, 1082.
  (c) Bokka, A.; Jeon, J. Org. Lett. 2016, 18, 5324.
8. [8]
  (a) Millan, A.; Towns, E.; Maitlis, P. M. J. Chem. Soc., Chem. Commun. 1981, 673.
  (b) Millan, A.; Fernandez, M.-J.; Bentz, P.; Maitlis, P. M. J. Mol. Catal. 1984, 26, 89.
  (c) Doyle, M. P.; Devora, G. A.; Nefedov, A. O.; High, K. G. Organometallics 1992, 11, 549.
  (d) Takeuchi, R.; Yasue, H. Organometallics 1996, 15, 2098.
  (e) Truscott, B. J.; Slawin, A. M. Z.; Nolan, S. P. Dalton Trans. 2013, 42, 270.
9. [9]
  LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906. doi: 10.1021/ja962979n
10. [10]
  (a) Fernández, M. J.; Esteruelas, M. A.; Jlménez, M. S.; Oro, L. A. Organometallics 1986, 5, 1519.
  (b) Oro, L. A.; Fernandez, M. J.; Esteruelas, M. A.; Jimenez, M. S. J. Mol. Catal. 1986, 37, 151.
  (c) Tanke, R. S.; Crabtree, R. H. Organometallics 1991, 10, 415.
  (d) Lu, B.; Falck, J. R. J. Org. Chem. 2010, 75, 1701.
  (e) Cheng, C.; Simmons, E. M.; Hartwig, J. F. Angew. Chem., Int. Ed. 2013, 52, 8984.
11. [11]
  Sprengers, J. W.; de Greef, M.; Duin, M. A.; Elsevier, C. J. Eur. J. Inorg. Chem. 2003, 3811.
12. [12]
  Jiang, Y.; Blacque, O.; Fox, T.; Frech, C. M.; Berke, H. Chem.-Eur. J. 2009, 15, 2121. doi: 10.1002/chem.v15:9
13. [13]
  Nakamura, S.; Yonehara, M.; Uchiyama, M. Chem.-Eur. J. 2008, 14, 1068. doi: 10.1002/(ISSN)1521-3765
14. [14]
  (a) Sun, J.; Deng, L. ACS Catal. 2016, 6, 290.
  (b) Du, X.-Y.; Huang, Z. ACS Catal. 2017, 7, 1227.
  (c) Zhang, J.-H.; Hao, X.-Q.; Wang, Z.-L.; Ren, C.-J.; Niu, J.-L.; Song, M.-P. Chin. J. Org. Chem. 2017, 37, 1237 (in Chinese).
  (张家恒, 郝新奇, 王正龙, 任常久, 牛俊龙, 宋毛平, 有机化学, 2017, 37, 1237.)
  (d) Gu, Z.-Y.; Ji, S.-J. Acta Chim. Sinica 2018, 76, 347 (in Chinese).
  (顾正洋, 纪顺俊, 化学学报, 2018, 76, 347.)
15. [15]
  Nesmeyanov, A. N.; Freidlina, R. K.; Chukovskaya, E. C.; Petrova, R. G.; Belyavsky, A. B. Tetrahedron 1962, 17, 61. doi: 10.1016/S0040-4020(01)99004-0
16. [16]
  (a) Kakiuchi, F.; Tanaka, Y.; Chatani, N.; Murai, S. J. Organomet. Chem. 1993, 456, 45.
  (b) Naumov, R. N.; Itazaki, M.; Kamitani, M.; Nakazawa, H. J. Am. Chem. Soc. 2012, 134, 804.
  (c) Marciniec, B.; Kownacka, A.; Kownacki, I.; Taylor, R. Appl. Catal. A: General 2014, 486, 230.
  (d) Sunada, Y.; Noda, D.; Soejima, H.; Tsutsumi, H.; Nagashima, H. Organometallics 2015, 34, 2896.
  (e) Du, X.-Y.; Zhang, Y.-L.; Peng, D.-J.; Huang, Z. Angew. Chem., Int. Ed. 2016, 55, 6671.
17. [17]
  (a) Marciniec, B.; Maciejewski, H.; Kownacki, I. J. Mol. Catal. A: Chemical 1998, 135, 223.
  (b) Maciejewski, H.; Marciniec, B.; Kownacki, I. J. Organomet. Chem. 2000, 597, 175.
18. [18]
  Takeshita, K.; Seki, Y.; kawamoto, K.; Murai, S.; Sonoda, N. J. Org. Chem. 1987, 52, 4864. doi: 10.1021/jo00231a008
19. [19]
  Atienza, C. C. H.; Diao, T.; Weller, K. J.; Nye, S. A.; Lewis, K. M.; Delis, J. G. P.; Boyer, J. L.; Roy, A. K.; Chirik, P. J. J. Am. Chem. Soc. 2014, 136, 12108. doi: 10.1021/ja5060884
20. [20]
  Gorczyński, A.; Zaranek, M.; Witomska, S.; Bocian, A.; Stefankiewicz, A. R.; Kubicki, M.; Patroniak, V.; Pawluć, P. Catal. Commun. 2016, 78, 71. doi: 10.1016/j.catcom.2016.02.009
21. [21]
  (a) Wang, C.; Teo, W. J.; Ge, S.-Z. ACS Catal. 2017, 7, 855.
  (b) Liu, Y.; Deng, L. J. Am. Chem. Soc. 2017, 139, 1798.
  (c) Gao, Y.-F.; Wang, L.-J.; Deng, L. ACS Catal. 2018, 8, 9637.
  (d) Basu, D.; Gilbert-Wilson, R.; Gray, D. L.; Rauchfuss, T. B. Organometallics 2018, 37, 2760.
  (e) Sanagawa, A.; Nagashima, H. Organometallics 2018, 37, 2859.
22. [22]
  For selected reviews on earth-abundant transition metal-catalyzed asymmetric hydrofunctionalization of alkenes and alkynes, see:
  (a) Chen, J.-H.; Lu, Z. Org. Chem. Front. 2018, 5, 260.
  (b) Chen, J.-H.; Guo, J.; Lu, Z. Chin. J. Chem. 2018, 36, 1075.
23. [23]
  For hydroboration of alkenes and alkynes, see: (a) Chen, J.-H.; Xi, T.; Lu, Z. Org. Lett. 2014, 16, 6452.
  (b) Chen, J.-H.; Xi, T.; Ren, X.; Cheng, B.; Guo, J.; Lu, Z. Org. Chem. Front. 2014, 1, 1306.
  (c) Zhang, H.-Y.; Lu, Z. ACS Catal. 2016, 6, 6596.
  (d) Xi, T.; Lu, Z. ACS Catal. 2017, 7, 1181.
  (e) Chen, X.; Cheng, Z.-Y.; Lu, Z. Org. Lett. 2017, 19, 969.
  (f) Chen, C.-H.; Shen, X.-Z.; Chen, J.-H.; Hong, X.; Lu, Z. Org. Lett. 2017, 19, 5422.
  (g) Guo, J.; Cheng, B.; Shen, X.-Z.; Lu, Z. J. Am. Chem. Soc. 2017, 139, 15316.
  (h) Chen, X.; Cheng, Z.-Y.; Guo, J.; Lu, Z. Nat. Commun. 2018, 9, 3939.
24. [24]
  For hydrosilylation of alkenes and alkynes, see:
  (a) Chen, J.-H.; Cheng, B.; Cao, M.-Y.; Lu, Z. Angew. Chem., Int. Ed. 2015, 54, 4661.
  (b) Guo, J.; Lu, Z. Angew. Chem., Int. Ed. 2016, 55, 10835.
  (c) Xi, T.; Lu, Z. J. Org. Chem. 2016, 81, 8858.
  (d) Guo, J.; Shen, X.-Z.; Lu, Z. Angew. Chem., Int. Ed. 2017, 56, 615.
  (e) Cheng, B.; Lu, P.; Zhang, H.-Y.; Cheng, X.-P.; Lu, Z. J. Am. Chem. Soc. 2017, 139, 9439.
  (f) Cheng, B.; Liu, W.-B.; Lu, Z. J. Am. Chem. Soc. 2018, 140, 5014.
  (g) Cheng, Z.-Y.; Xing, S.-P.; Guo, J.; Cheng, B.; Hu, L.-F.; Zhang, X.-H.; Lu, Z. Chin. J. Chem. 2019, 37, 457.
  (h) Guo, J.; Wang, H.-L.; Xing, S.-P. Hong, X.; Lu, Z. Chem 2019, 5, 881.
25. [25]
  For asymmetric hydrogenation of alkenes, see:Chen, J.-H.; Chen, C.-H.; Ji, C.-L.; Lu, Z. Org. Lett. 2016, 18, 1594.
26. [26]
  Zhang, L.; Zuo, Z.-Q.; Wan, X.-L.; Huang, Z. J. Am. Chem. Soc. 2014, 136, 15501. doi: 10.1021/ja5093908
27. [27]
  Komiyama, T.; Minami, Y.; Hiyama, T. ACS Catal. 2017, 7, 631. doi: 10.1021/acscatal.6b02374
28. [28]
  Guo, J.; Chen, J.-H.; Lu, Z. Chem. Commun. 2015, 51, 5725. doi: 10.1039/C5CC01084E
29. [29]
  JoongLee, S.; KyeuPark, M.; HeeHan, B. Silicon Chemistry 2002, 1, 41. doi: 10.1023/A:1016032911342
30. [30]
  Ramírez-Oliva, E.; Hernández, A.; Martínez-Rosales, J. M.; Aguilar-Elguezabal, A.; Herrera-Pérez, G.; Cervantes, J. ARKIVOC 2006, 126.
31. [31]
  Karabelas, K.; Hallberg, A. J. Org. Chem. 1986, 51, 5286. doi: 10.1021/jo00376a044
1. [1]
  Kun Tang , Fen Su , Shijie Pan , Fengfei Lu , Zhongfu Luo , Fengrui Che , Xingxing Wu , Yonggui Robin Chi . Enones from aldehydes and alkenes by carbene-catalyzed dehydrogenative couplings. Chinese Chemical Letters, 2024, 35(9): 109495-. doi: 10.1016/j.cclet.2024.109495
2. [2]
  Fan Chen , Xiaoyu Zhao , Weihang Miao , Yingying Li , Ye Yuan , Lingling Chu . Regio- and enantioselective hydrofluorination of internal alkenes via nickel-catalyzed hydrogen atom transfer. Chinese Chemical Letters, 2025, 36(5): 110239-. doi: 10.1016/j.cclet.2024.110239
3. [3]
  Zhenkang Ai , Hui Chen , Xuebin Liao . Nickel-catalyzed decarboxylative difluoromethylation and alkylation of alkenes. Chinese Chemical Letters, 2025, 36(3): 109954-. doi: 10.1016/j.cclet.2024.109954
4. [4]
  Yunqiang Li , Yongxian Huang , Sinuo Li , He Huang , Zhiwei Jiao . Elaborating azaaryl alkanes enabled by photoredox/palladium dual catalyzed dialkylation of azaaryl alkenes. Chinese Chemical Letters, 2025, 36(4): 110051-. doi: 10.1016/j.cclet.2024.110051
5. [5]
  Lei Wan , Yizhou Tong , Xi Lu , Yao Fu . Cobalt-catalyzed reductive alkynylation to construct C(sp)-C(sp³) and C(sp)-C(sp²) bonds. Chinese Chemical Letters, 2024, 35(7): 109283-. doi: 10.1016/j.cclet.2023.109283
6. [6]
  Peng Guo , Shicheng Dong , Xiang-Gui Zhang , Bing-Bin Yang , Jun Zhu , Ke-Yin Ye . Cobalt-catalyzed migratory carbon-carbon cross-coupling of borabicyclo[3.3.1]nonane (9-BBN) borates. Chinese Chemical Letters, 2025, 36(4): 110052-. doi: 10.1016/j.cclet.2024.110052
7. [7]
  Er-Meng Wang , Ziyi Wang , Xu Ban , Xiaowei Zhao , Yanli Yin , Zhiyong Jiang . Chemoselective photocatalytic sulfenylamination of alkenes with sulfenamides via energy transfer. Chinese Chemical Letters, 2024, 35(12): 109843-. doi: 10.1016/j.cclet.2024.109843
8. [8]
  Xingfen Huang , Jiefeng Zhu , Chuan He . Catalytic enantioselective N-silylation of sulfoximine. Chinese Chemical Letters, 2024, 35(4): 108783-. doi: 10.1016/j.cclet.2023.108783
9. [9]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
10. [10]
  Boqiang Wang , Yongzhuo Xu , Jiajia Wang , Muyang Yang , Guo-Jun Deng , Wen Shao . Transition-metal free trifluoromethylimination of alkenes enabled by direct activation of N-unprotected ketimines. Chinese Chemical Letters, 2024, 35(9): 109502-. doi: 10.1016/j.cclet.2024.109502
11. [11]
  Chonglong He , Yulong Wang , Quan-Xin Li , Zichen Yan , Keyuan Zhang , Shao-Fei Ni , Xin-Hua Duan , Le Liu . Alkylarylation of alkenes with arylsulfonylacetate as bifunctional reagent via photoredox radical addition/Smiles rearrangement cascade. Chinese Chemical Letters, 2025, 36(5): 110253-. doi: 10.1016/j.cclet.2024.110253
12. [12]
  Xiao-Ming Chen , Lianhui Song , Jun Pan , Fei Zeng , Yi Xie , Wei Wei , Dong Yi . Visible-light-induced four-component difunctionalization of alkenes to construct phosphorodithioate-containing quinoxalin-2(1H)-ones. Chinese Chemical Letters, 2024, 35(11): 110112-. doi: 10.1016/j.cclet.2024.110112
13. [13]
  Huaixiang Yang , Miao-Miao Li , Aijun Zhang , Jiefei Guo , Yongqi Yu , Wei Ding . Visible-light-induced photocatalyst- and metal-free radical phosphinoyloximation of alkenes with tert-butyl nitrite as bifunctional reagent. Chinese Chemical Letters, 2025, 36(3): 110425-. doi: 10.1016/j.cclet.2024.110425
14. [14]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
15. [15]
  Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi . Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand. Chinese Chemical Letters, 2024, 35(7): 109292-. doi: 10.1016/j.cclet.2023.109292
16. [16]
  Jiayi Guo , Liangxiong Ling , Qinwei Lu , Yi Zhou , Xubiao Luo , Yanbo Zhou . Degradation of chloroxylenol by CoS_x activated peroxomonosulfate: Role of cobalt-sulfur ratio. Chinese Chemical Letters, 2025, 36(4): 110380-. doi: 10.1016/j.cclet.2024.110380
17. [17]
  Jun-Jie Fang , Yun-Peng Xie , Xing Lu . Organooxotin and cobalt/manganese heterometallic nanoclusters exhibiting single-molecule magnetism. Chinese Journal of Structural Chemistry, 2025, 44(4): 100515-100515. doi: 10.1016/j.cjsc.2025.100515
18. [18]
  Fengqing Wang , Changxing Qi , Chunmei Chen , Qin Li , Qingyi Tong , Weiguang Sun , Zhengxi Hu , Minyan Wang , Hucheng Zhu , Lianghu Gu , Yonghui Zhang . Discovery and enantioselective total synthesis of antitumor agent asperfilasin A via a regio- and diastereoselective Nazarov cyclization. Chinese Chemical Letters, 2025, 36(6): 110252-. doi: 10.1016/j.cclet.2024.110252
19. [19]
  Xinyu Huai , Jingxuan Liu , Xiang Wu . Cobalt-Doped NiMoO4 Nanosheet for High-performance Flexible Supercapacitor. Chinese Journal of Structural Chemistry, 2023, 42(10): 100158-100158. doi: 10.1016/j.cjsc.2023.100158
20. [20]
  Abiduweili Sikandaier , Yukun Zhu , Dongjiang Yang . In-situ decorated cobalt phosphide cocatalyst on Hittorf's phosphorus triggering efficient photocatalytic hydrogen production. Chinese Journal of Structural Chemistry, 2024, 43(2): 100242-100242. doi: 10.1016/j.cjsc.2024.100242

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(724)
HTML views(110)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142