Citation: Lü Xiaomei, Ruan Jiancheng, Chen Xinzhi, Qian Chao. Cross-Linked Chitosan Bead Supported Copper Complex in Water as a Green and Efficient Catalytic Protocol for Ullmann Reaction[J]. Chinese Journal of Organic Chemistry, ;2019, 39(6): 1720-1726. doi: 10.6023/cjoc201901018 shu

Cross-Linked Chitosan Bead Supported Copper Complex in Water as a Green and Efficient Catalytic Protocol for Ullmann Reaction

a.
Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027
b.
School of Chemical and Biomedical Engineering, College of Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459, Singapore

Corresponding author: Qian Chao, qianchao@zju.edu.cn
Received Date: 14 January 2019
Revised Date: 25 March 2019
Available Online: 11 June 2019
Fund Project: the National Natural Science Foundation of China 21476194Project supported by the National Natural Science Foundation of China (No. 21476194), and the National Key Research and Development Program of China (No. 2016YFB0301800)the National Key Research and Development Program of China 2016YFB0301800

Figures(7)

A green, efficient, and recyclable catalytic protocol for Ullmann C-N reaction in water was developed. The catalyst Chi-Gly@CuI was prepared by the cross-linking reaction of chitosan bead with glyoxal and subsequently anchored with copper salt. Chi-Gly@CuI bead of 0.3 mm in mean diameter possesses porous micro-structure demonstrated by scanning electron microscope (SEM). The structure of Chi-Gly@CuI was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES), and X-ray photoelectron spectroscopy (XPS). This catalytic protocol for Ullmann reaction in water exhibited high applicability, from which the corresponding coupling products were afforded in good to excellent yields. Chi-Gly@CuI could be easily separated from products by simple filtration almost without weight loss. Most notably, after 10 times of recycling, its catalytic activity and chemical stability were still maintained.
- cross-linked chitosan bead,
- Ullmann reaction,
- copper,
- heterogenous catalysis,
- in water
1. [1]
  Ferlin, F.; Trombettoni, V.; Luciani, L.; Fusi, S.; Piermatti, O.; Santoro, S.; Vaccaro, L. Green Chem. 2018, 20, 1634. doi: 10.1039/C8GC00287H
2. [2]
  Bariwal, J.; Van der Eycken, E. Chem. Soc. Rev. 2013, 42, 9283. doi: 10.1039/c3cs60228a
3. [3]
  Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2009, 48, 6954. doi: 10.1002/anie.v48:38
4. [4]
  Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem Rev 2002, 102, 1359. doi: 10.1021/cr000664r
5. [5]
  Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. Rev. 2004, 248, 2337. doi: 10.1016/j.ccr.2004.09.014
6. [6]
  Sambiagio, C.; Marsden, S. P.; Blacker, A. J.; McGowan, P. C. Chem. Soc. Rev. 2014, 43, 3525. doi: 10.1039/C3CS60289C
7. [7]
  Monnier, F.; Taillefer, M., Angew. Chem., Int. Ed. 2008, 47, 3096. doi: 10.1002/(ISSN)1521-3773
8. [8]
  Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046. doi: 10.1002/(ISSN)1521-3773
9. [9]
  Klapars, A.; Antilla, J. C.; Huang, X. H.; Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727. doi: 10.1021/ja016226z
10. [10]
  Job, G. E.; Buchwald, L. Org. Lett. 2002, 4, 3703. doi: 10.1021/ol026655h
11. [11]
  Klapars, A.; Huang, X. H.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 7421. doi: 10.1021/ja0260465
12. [12]
  Ma, D. W.; Cai, Q. Synlett 2004, (1), 128. doi: 10.1055/s-2003-44995
13. [13]
  Cheng, D. P.; Gan, F. F.; Qian, W. X.; Bao, W. L. Green Chem. 2008, 10, 171. doi: 10.1039/B713658G
14. [14]
  Kwong, F. Y.; Klapars, A.; Buchwald, S. L. Org. Lett. 2002, 4, 581. doi: 10.1021/ol0171867
15. [15]
  Kwong, F. Y.; Buchwald, S. L. Org. Lett. 2003, 5, 793. doi: 10.1021/ol0273396
16. [16]
  Antilla, J. C.; Baskin, J. M.; Barder, T. E.; Buchwald, S. L. J. Org. Chem. 2004, 69, 5578. doi: 10.1021/jo049658b
17. [17]
  Cristau, H. J.; Cellier, P. P.; Spindler, J. F.; Taillefer, M. Chem.-Eur. J. 2004, 10, 5607. doi: 10.1002/(ISSN)1521-3765
18. [18]
  Choudary, B. M.; Sridhar, C.; Kantam, M. L.; Venkanna, G. T.; Sreedhar, B. J. Am. Chem. Soc. 2005, 127, 9948. doi: 10.1021/ja0436594
19. [19]
  Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4120. doi: 10.1021/ja050120c
20. [20]
  Zhang, H.; Cai, Q.; Ma, D. W. J. Org. Chem. 2005, 70, 5164. doi: 10.1021/jo0504464
21. [21]
  Zhu, W.; Ma, D. W. J. Org. Chem. 2005, 70, 2696. doi: 10.1021/jo047758b
22. [22]
  Shafir, A.; Buchwald, S. L. J. Am. Chem. Soc. 2006, 128, 8742. doi: 10.1021/ja063063b
23. [23]
  Ma, D. W.; Cai, Q. A. Acc. Chem. Res. 2008, 41, 1450. doi: 10.1021/ar8000298
24. [24]
  Cassez, A.; Ponchel, A.; Hapiot, F.; Monflier, E. Org. Lett. 2006, 8, 4823. doi: 10.1021/ol061836v
25. [25]
  Xue, C. H.; Palaniappan, K.; Arumugam, G.; Hackney, S. A.; Liu, J.; Liu, H. Y. Catal. Lett. 2007, 116, 94. doi: 10.1007/s10562-007-9108-7
26. [26]
  Ngah, W. S. W.; Fatinathan, S. Chem. Eng. J. 2008, 143, 62. doi: 10.1016/j.cej.2007.12.006
27. [27]
  Baig, R. B. N.; Varma, R. S. Green Chem. 2013, 15, 1839. doi: 10.1039/c3gc40401c
28. [28]
  Dekamin, M. G.; Azimoshan, M.; Ramezani, L. Green Chem. 2013, 15, 811. doi: 10.1039/c3gc36901c
29. [29]
  Zhang, G. F.; Luan, Y. X.; Han, X. W.; Wang, Y.; Wen, X.; Ding, C. R.; Gao, J. R. Green Chem. 2013, 15, 2081. doi: 10.1039/c3gc40645h
30. [30]
  Baig, R. B. N.; Nadagouda, M. N.; Varma, R. S. Green Chem. 2014, 16, 2122. doi: 10.1039/c3gc42004c
31. [31]
  Shen, C.; Xu, J.; Yu, W. B.; Zhang, P. F. Green Chem. 2014, 16, 3007. doi: 10.1039/C4GC00161C
32. [32]
  Yang, B.; Mao, Z. X.; Zhu, X. H.; Wan, Y. Q. Catal. Commun. 2015, 60, 92. doi: 10.1016/j.catcom.2014.11.014
33. [33]
  Cui, Q.; Zhao, H.; Luo, G.; Xu, J. Ind. Eng. Chem. Res. 2017, 56, 143. doi: 10.1021/acs.iecr.6b04077
34. [34]
  Ma, L.; Su, Y.; Chen, J.; Xu, J. Ind. Eng. Chem. Res. 2017, 56, 12655. doi: 10.1021/acs.iecr.7b03667
35. [35]
  Su, Y.; Ma, L.; Chen, J.; Xu, J. Carbohydr. Polym. 2017, 175, 113. doi: 10.1016/j.carbpol.2017.07.052
36. [36]
  Tong, J. H.; Zhen, L.; Xia, C. G. J. Mol. Catal. A 2005, 231(1-2), 197. doi: 10.1016/j.molcata.2005.01.011
37. [37]
  Anuradha; Kumari, S.; Pathak, D. D. Tetrahedron Lett. 2015, 56, 4135. doi: 10.1016/j.tetlet.2015.05.049
38. [38]
  Keshipour, S.; Mirmasoudi, S. S. Carbohydr. Polym. 2018, 196, 494. doi: 10.1016/j.carbpol.2018.05.068
39. [39]
  Gioia, C.; Ricci, A.; Bernardi, L.; Bourahla, K.; Tanchoux, N.; Robitzer, M.; Quignard, F. Eur. J. Org. Chem. 2013, (3), 588.
40. [40]
  Chanda, A.; Fokin, V. V. Chem. Rev. 2009, 109, 725. doi: 10.1021/cr800448q
41. [41]
  Krause, N. Curr. Opin. Green Sustainable Chem. 2017, 7, 18. doi: 10.1016/j.cogsc.2017.06.009
42. [42]
  La Sorella, G.; Strukul, G.; Scarso, A. Green Chem 2015, 17, 644. doi: 10.1039/C4GC01368A
43. [43]
  Lipshutz, B. H.; Ghorai, S.; Cortes-Clerget, M. Chemistry 2018, 24, 6672. doi: 10.1002/chem.v24.26
44. [44]
  Rani, D.; Singla, P.; Agarwal, J. Carbohydr. Polym. 2018, 202, 355. doi: 10.1016/j.carbpol.2018.09.008
45. [45]
  Ge, X.; Qian, C.; Chen, X. Z. Tetrahedron:Asymmetry 2014, 25, 1450. doi: 10.1016/j.tetasy.2014.10.003
46. [46]
  Ge, X.; Qian, C.; Chen, Y. B.; Chen, X. Z. Tetrahedron:Asymmetry 2014, 25, 596. doi: 10.1016/j.tetasy.2014.03.015
47. [47]
  Ge, X.; Chen, X. Z.; Qian, C.; Zhou, S. D. RSC Adv. 2016, 6, 58898. doi: 10.1039/C6RA13536F
48. [48]
  Ge, X.; Chen, X. Z.; Qian, C.; Zhou, S. D. RSC Adv. 2016, 6, 29638. doi: 10.1039/C6RA03015G
49. [49]
  Ge, X.; Sun, F.; Liu, X.; Chen, X.; Qian, C.; Zhou, S. New J. Chem. 2017, 41, 13175. doi: 10.1039/C7NJ02784B
50. [50]
  Liu, X.; Chang, S.; Chen, X.; Ge, X.; Qian, C. New J. Chem. 2018, 42, 16013. doi: 10.1039/C8NJ02677G
51. [51]
  Sowmya, A.; Meenakshi, S. Int. J. Biol. Macromol. 2014, 64, 224. doi: 10.1016/j.ijbiomac.2013.11.036
52. [52]
  Saha, S.; Das, S.; Sen, D.; Ghorai, U. K.; Mazumder, N.; Gupta, B. K.; Chattopadhyay, K. K. J. Mater. Chem. C 2015, 3, 6786. doi: 10.1039/C5TC00719D
53. [53]
  Kumar, M.; Bhatt, V.; Nayal, O. S.; Sharma, S.; Kumar, V.; Thakur, M. S.; Kumar, N.; Bal, R.; Singh, B.; Sharma, U. Catal. Sci. Technol. 2017, 7, 2857. doi: 10.1039/C7CY00832E
54. [54]
  Zeng, L. X.; Chen, Y. F.; Zhang, Q. Y.; Guo, X. M.; Peng, Y. N.; Xiao, H. J.; Chen, X. C.; Luo, J. W. Carbohydr. Polym. 2015, 130, 333. doi: 10.1016/j.carbpol.2015.05.015
55. [55]
  Zhou, Y. T.; Branford-White, C.; Nie, H. L.; Zhu, L. M. Colloid Surface B 2009, 74, 244. doi: 10.1016/j.colsurfb.2009.07.026
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