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

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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
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