Citation: Bai Yali, Li Xiaowei, Xiao Xuedong, Liu Jiaqi, Yang Junjuan, Wang Junwen. Synthesis of Imidazolium Precursors for the Hydroxyl-Group-Modified N-Heterocyclic Carbenes and Applications of the in situ Generated Carbene Ligands in Suzuki-Miyaura and Sonogashira Coupling Reactions[J]. Chinese Journal of Organic Chemistry, ;2017, 37(5): 1258-1265. doi: 10.6023/cjoc201610039 shu

Synthesis of Imidazolium Precursors for the Hydroxyl-Group-Modified N-Heterocyclic Carbenes and Applications of the in situ Generated Carbene Ligands in Suzuki-Miyaura and Sonogashira Coupling Reactions

Bai Yali ^a ,
Li Xiaowei ^b ,
Xiao Xuedong ^a ,
Liu Jiaqi ^a ,
Yang Junjuan ^a ,
Wang Junwen ^a,*,,

a.
Department of Chemistry, Shanxi Normal University, Linfen 041000
b.
Inner Mongolia Datang International Renewable Resources Development Co. Ltd., Hohhot 010000

Corresponding author: Wang Junwen, wangjunwen2013@126.com
Received Date: 22 October 2016
Revised Date: 6 December 2016

Fund Project: Project supported by the Basic Research Project of Shanxi Province of China 2015011029and the Shanxi Province Education Innovation Project for Postgraduate 2015BY38the Undergraduate Innovative Experiment Program of Shanxi Normal University SD2014CXXM-36

Figures(4)

Four imidazolium precursors for the N-heterocyclic carbenes (NHCs) with a hydroxyl functionalized four-mem-bered heterocyclic side arm were synthesized and characterized by IR, XRD and NMR spectroscopies. The corresponding NHC ligands thus generated in situ from these imidazolium precursors in the presence of base such as KOH, together with PdCl₂(CH₃CN)₂, exhibited excellent catalytic activity in Suzuki-Miyaura cross-coupling reactions for the synthesis of a range of biaryl compounds. The reactions could be conducted in the mixed solvent of tert-butyl alcohol/water (V:V=1:1) at room temperature with the advantages of mild conditions, high efficiency as well as environmental friendliness. In addition, although in minor amount, the mixed catalyst system containing imidazolium salts, PdCl₂(CH₃CN)₂ (0.1%) and CuI (1%) exhibited excellent catalytic activity in Sonogashira coupling reaction. In particular, the combination system of PdCl₂/imidazolium salt 3b has been shown to be higher catalytically active for both coupling reactions.
- hydroxyl group,
- N-heterocyclic carbene,
- palladium,
- Suzuki-Miyaura cross-coupling,
- Sonogashira cross-coupling
1. [1]
  Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361. doi: 10.1021/ja00001a054
2. [2]
  Qu, M. N.; He, J. M. Chin. J. Org. Chem. 2011, 31, 1388 (in Chinese).
3. [3]
  Tang, Y.; Yang, F. F.; Nie, S. P.; Wang, L.; Luo, Z. B.; Lu, H. F. Chin. J. Org. Chem. 2015, 35, 705 (in Chinese).
4. [4]
  Zhang, D.; Zi, G. F. Chem. Soc. Rev. 2015, 44, 1898. doi: 10.1039/C4CS00441H
5. [5]
  Barroso, S.; de Aguiar, S. R. M. M.; Munhá, R. F.; Martins, A. M. J. Organomet. Chem. 2014, 760, 60. doi: 10.1016/j.jorganchem.2013.11.041
6. [6]
  Zhao, N.; Hou, G. H.; Deng, X. B.; Zi, G. F.; Walter, M. D. Dalton Trans. 2014, 43, 8261. doi: 10.1039/C4DT00510D
7. [7]
  Hameury, S.; de Frémont, P.; Breuil, P. A. R.; Olivier-Bourbigou, H.; Braunstein, P. Inorg. Chem., 2014, 53, 5189. doi: 10.1021/ic500349t
8. [8]
  Ohmiya, H.; Zhang, H.; Shibata, S.; Harada, A.; Sawamura, M. Angew. Chem. 2016, 128, 4855. doi: 10.1002/ange.201600619
9. [9]
10. [10]
  Fortman, G. C.; Nolan, S. P. Chem. Soc. Rev. 2011, 40, 5151. doi: 10.1039/c1cs15088j
11. [11]
  Levin, E.; Ivry, E.; Diesendruck, C. E.; Lemcoff, N. G. Chem. Rev. 2015, 115, 4607. doi: 10.1021/cr400640e
12. [12]
  Schmid, T. E.; Jones, D. C.; Songis, O.; Diebolt, O.; Furst, M. R. L.; Slawin, A. M. Z.; Cazin, C. S. J. Dalton Trans. 2013, 42, 7345. doi: 10.1039/c2dt32858e
13. [13]
  Neumann, K. T.; Laursen, S. R.; Lindhardt, A. T.; Bang-Andersen, B.; Skrydstrup, T. Org. Lett. 2014, 16, 2216. doi: 10.1021/ol5007289
14. [14]
  Caddick, S.; Cloke, F. G. N.; Clentsmith, G. K. B.; Hitchcock, P. B.; McKerrecher, D.; Titcomb, L. R.; Williams, M. R. V. J. Organomet. Chem. 2001, 617, 635.
15. [15]
  Burkhard, J. A.; Wagner, B.; Fischer, H.; Schuler, F.; Müller, K.; Carreira, E. M. Angew. Chem., Int. Ed. 2010, 49, 3524. doi: 10.1002/anie.200907108
16. [16]
  Burkhard, J. A.; Guérot, C.; Knust, H.; Rogers-Evans, M.; Carreira, E. M. Org. Lett. 2010, 12, 1944. doi: 10.1021/ol1003302
17. [17]
  Burkhard, J.; Carreira, E. M. Org. Lett. 2008, 10, 3525. doi: 10.1021/ol801293f
18. [18]
  Wuitschik, G.; Rogers-Evans, M.; Buckl, A.; Bernasconi, M.; Märki, M.; Godel, T.; Fischer, H.; Wagner, B.; Parrilla, I.; Schuler, F.; Schneider, J.; Alker, A.; Schweizer, W. B.; Müller, K.; Carreira, E. M. Angew. Chem. 2008, 120, 4588. doi: 10.1002/(ISSN)1521-3757
19. [19]
  Wang, J. W.; Li, Q. S.; Xu, F. B.; Song, H. B.; Zhang, Z. Z. Eur. J. Org. Chem. 2006, 1310.
20. [20]
  Yu, L.; Han, Z. Mater. Lett. 2016, 184, 312. doi: 10.1016/j.matlet.2016.08.056
21. [21]
  Al-Amin, M.; Akimoto, M.; Tameno, T.; Ohki, Y.; Takahashi, N.; Hoshiya, N.; Shuto, S.; Arisawa, M. Green Chem. 2013, 15, 1142. doi: 10.1039/c3gc00063j
22. [22]
  Ma, H. C.; Cao, W.; Bao, Z. K.; Lei, Z. Q. Catal. Sci. Technol. 2012, 2, 2291. doi: 10.1039/c2cy20126g
23. [23]
  Zhao, X. H.; Zhao, Y. Y.; Zhang, J.; Li, X. Appl. Organomet. Chem. 2015, 29, 840. doi: 10.1002/aoc.3391
24. [24]
  Yadav, R. R.; Vishwakarma, R. A.; Bharate, S. B. Tetrahedron Lett. 2012, 53, 5958. doi: 10.1016/j.tetlet.2012.08.121
25. [25]
  Hassine, A.; Sebti, S.; Solhy, A.; Zahouily, M.; Len, C.; Hedhili, M. N.; Fihri, A. Appl. Catal., A 2013, 450, 13. doi: 10.1016/j.apcata.2012.09.046
26. [26]
  Siamaki, A. R.; Lin, Y.; Woodberry, K.; Connell, J. W.; Gupton, B. F. J. Mater. Chem. A 2013, 1, 12909.
27. [27]
  Iranpoor, N.; Firouzabadi, H.; Motevalli, S.; Rajabi, K. Aust. J. Chem. 2015, 68, 926. doi: 10.1071/CH14332
28. [28]
  Zhang, G. P.; Li, P. H. Chin. J. Org. Chem. 2010, 30, 117 (in Chinese).
29. [29]
  Elumalai, V.; Bjørsvik, H. R. Tetrahedron Lett. 2016, 57, 1224. doi: 10.1016/j.tetlet.2016.02.007
30. [30]
  Wang, X.; Wang, Z. H.; Wu, Y.; Luo, Y. L.; Zhang, G. F.; Jian, Y. J.; Sun, H. M.; Zhang, W. Q.; Gao, Z. W. Appl. Organomet. Chem. 2016, 30, 831. doi: 10.1002/aoc.v30.10
31. [31]
  Sagadevan, A.; Hwang, K. C. Adv. Synth. Catal. 2012, 354, 3421. doi: 10.1002/adsc.v354.18
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