Citation: Zhang Yiwei, Chen Yilin, Fang Xiaolong, Yuan Youzhu, Zhu Hongping. Advances for the Ruthenium Complexes-Based Homogeneous Catalytic Hydrogenation of Oxalates to Ethylene Glycol[J]. Chinese Journal of Organic Chemistry, ;2017, 37(9): 2275-2286. doi: 10.6023/cjoc201703021 shu

Advances for the Ruthenium Complexes-Based Homogeneous Catalytic Hydrogenation of Oxalates to Ethylene Glycol

State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Corresponding author: Yuan Youzhu, yzyuan@xmu.edu.cn Zhu Hongping, hpzhu@xmu.edu.cn
Received Date: 10 March 2017
Revised Date: 2 May 2017
Available Online: 17 September 2017
Fund Project: Project supported by the National Natural Science Foundation of China (Nos. 21473142, 91545115, 21473145) and the Innovative Research Team of China (Nos. IRT_14R31, J1310024)Innovative Research Team of China IRT_14R31National Natural Science Foundation of China 21473145Innovative Research Team of China J1310024National Natural Science Foundation of China 91545115National Natural Science Foundation of China 21473142

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Hydrogenation of oxalates is one of the important organic reactions, which has an ultimate use for the industrial production of ethylene glycol. The studies on the ruthenium complexes-based homogeneous catalytic reaction systems are herein summarized. With the focus on the catalytic reaction systems, the important factors with significant influences on the oxalate transformation efficiency as well as the product selectivity are discussed, including temperature, H₂ pressure, catalyst concentration, reaction duration, additives, and so on. The catalytic reaction mechanisms are also discussed in detail, where the mechanism for the H₂-heterolysis promoted under the metal-ligand cooperation for the oxalate hydrogenation to ethylene glycol is enhanced. This study would be useful for designing the new catalyst applicable in industry.
- hydrogenation of oxalate,
- ruthenium complexes-based homogeneous catalytic system,
- ethylene glycol,
- reaction conditions,
- catalytic mechanism
1. [1]
2. [2]
3. [3]
  (a) Gaylord, N. G. J. Chem. Educ. 1957, 34, 367.
  (b) Hudlicky, M. Reductions in Organic Chemistry, ACS, Washington, DC, 1996.
4. [4]
  (a) Modler, R. F.; Gubler, R.; Inoguchi, Y. Detergent Alchols, CEH Marketing Research Report, 2004.
  (b) Hong, W. S. Natural Detergent Alcohols by a Vapour Phase Ester Hydrogenation Process, PPP Review 93-2-1, 2004.
  (c) Cant, N. W.; Trimm, D. L.; Turek, T. Catal. Rev. Sci. Eng. 1994, 36, 645.
5. [5]
  March, J. Advanced Organic Chemistry:Reactions Mechanisms and Structure, 4th ed., Wiley-Interscience, New York, 1992, p. 1213.
6. [6]
  (a) Rylander, P. N. Catalytic Hydrogenation in Organic Syntheses, Academic Press, New York, 1979.
  (b) de Vries, J. G.; Elsevier, C. J. Handbook of Heterogeneous Hydrogenation for Organic Synthesis, Weily-VCH, Weinheim, 2007.
7. [7]
8. [8]
  (a) Bayón, J. C.; Claver, C.; Masdeu-Bultó, A. M. WO 2003093208, 2003[Chem. Abstr. 2003, 139, 366612].
  (b) Pope, S. J. A.; Champness, N. R.; Reid, G. J. Chem. Soc., Dalton Trans. 1997, 1639.
9. [9]
  Seyden-Penne, J. Reductions by the Allumino-and Borohydride in Organic Synthesis, 2nd ed.; Wiley-VCH, New York, 1997.
10. [10]
  (a) Turek, T.; Trimm, D.; Cant, N. Catal. Rev. -Sci. Eng. 1994, 36, 645.
  (b) Pouilloux, Y.; Autin, F.; Barrault, J. Catal. Today 2000, 63, 87.
11. [11]
  Pritchard, J.; Filonenko, G. A.; van Putten, R.; Hensen, E. J. M.; Pidko, E. A. Chem. Soc. Rev. 2015, 44, 3808. doi: 10.1039/C5CS00038F
12. [12]
  (a) Grey, R. A.; Pez, G. P.; Wallo, A.; Corsi, J. J. Chem. Soc., Chem. Commun. 1980, 783.
  (b) Grey, R. A.; Pez, G. P.; Wallo, A. J. Am. Chem. Soc. 1981, 103, 7536.
  (c) De Graauw, C. F.; Peters, J. A.; van Bekkum, H.; Huskens, J. Synthesis 1994, 1007.
  (d) Ashby, E. C. Acc. Chem. Res. 1988, 21, 414.
13. [13]
  Matteoli, U.; Bianchi, M.; Menchi, G.; Frediani, P.; Piacenti, F. J. Mol. Catal. 1984, 22, 353. doi: 10.1016/0304-5102(84)80075-9
14. [14]
  (a) Matteoli, U.; Bianchi, M.; Menchi, G.; Frediani, P.; Piacenti, F. J. Mol. Catal. 1985, 29, 269.
  (b) Matteoli, U.; Menchi, G.; Bianchi, M.; Piacenti, F. J. Organomet. Chem. 1986, 299, 233.
  (c) Matteoli, U.; Bianchi, M.; Menchi, G.; Piacenti, F. J. Mol. Catal. 1988, 44, 347.
15. [15]
  (a) Matteoli, U.; Bianchi, M.; Menchi, G.; Piacenti, F. J. Mol. Catal. 1991, 64, 257.
  (b) Matteoli, U.; Menchi, G.; Bianchi, M.; Piacenti, F.; Ianelli, S.; Nardelli, M. J. Organomet. Chem. 1995, 498, 177.
16. [16]
  Teunissen, H. T.; Elsevier, C. J. Chem. Commun. 1997, 667.
17. [17]
  Kara, Y.; Wada, K. Chem. Lett. 1991, 20, 553. doi: 10.1246/cl.1991.553
18. [18]
  van Engelen, M. C.; Teunissen, H. T.; de Vries, J. G.; Elsevier, C. J. J. Mol. Catal. A:Chem. 2003, 206, 185. doi: 10.1016/S1381-1169(03)00427-8
19. [19]
  Boardman, B.; Hanton, M. J.; van Rensburg, H.; Tooze, R. P. Chem. Commun. 2006, 2289.
20. [20]
  Bayón, J. C.; Claver, C.; Masdeu-Bultó, A. M. Coord. Chem. Rev. 1999, 193~195, 73.
21. [21]
  Hanton, M. J.; Tin, S.; Boardman, B. J.; Miller, P. J. Mol. Catal. A:Chem. 2011, 346, 70. doi: 10.1016/j.molcata.2011.06.010
22. [22]
  Ziebart, C.; Jackstell, R.; Beller, M. ChemCatChem 2013, 5, 3228. doi: 10.1002/cctc.201300209
23. [23]
  Kuriyama, W.; Matsumoto, T.; Ogata, O.; Ino, Y.; Aoki, K.; Tanaka, S.; Ishida, K.; Kobayashi, T.; Sayo, N.; Saito, T. Org. Process Res. Dev. 2012, 16, 166. doi: 10.1021/op200234j
24. [24]
  Eveline, J.; Jongbloed, L. S.; Tromp, D. S.; Martin, L.; Bas, D. B.; Elsevier, C. J. ChemSusChem 2013, 6, 1737. doi: 10.1002/cssc.201300363
25. [25]
  (a) Bryndza, H. E.; Tam, W. Chem. Rev. 1988, 88, 1163.
  (b) Pàmies, O.; Bäckvall, J. E. Chem. Eur. J. 2001, 7, 5052.
  (c) Fulton, J. R.; Holland, A. W.; Fox, D. J.; Vergman, R. G. Acc. Chem. Res. 2002, 35, 44.
  (d) Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem. Rev. 2004, 248, 2201.
26. [26]
  (a) Yamakawa, M.; Ito, H.; Noyori, R. J. Am. Chem. Soc. 2000, 122, 1466.
  (b) Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40.
  (c) Ohkuma, T.; Koizumi, M.; Muñiz, K.; Hilt, G.; Kabuto, C.; Noyori, R. J. Am. Chem. Soc. 2002, 124, 6508.
  (d) Sandoval, C. A.; Ohkuma, T.; Muñiz, K.; Noyori, R. J. Am. Chem. Soc. 2003, 125, 13490.
27. [27]
  (a) Abdur-Rashid, K.; Clapham, S. E.; Hadzovic, A.; Harvey, J. N.; Lough, A. J.; Morris, R. H. J. Am. Chem. Soc. 2002, 124, 15104.
  (b) Abdur-Rashid, K.; Faatz, M.; Lough, A. J.; Morris, R. H. J. Am. Chem. Soc. 2001, 123, 7473.
  (c) Abbel, R.; Abdur-Rashid, K.; Faatz, M.; Hadzovic, A.; Lough, A. J.; Morris, R. H. J. Am. Chem. Soc. 2005, 127, 1870.
  (d) Abdur-Rashid, K.; Guo, R.; Lough, A. J.; Morris, R. H.; Song, D. Adv. Synth. Catal. 2005, 347, 571.
28. [28]
  (a) Hamilton, R. J.; Bergens, S. H. J. Am. Chem. Soc. 2006, 128, 13700.
  (b) Hamilton, R. J.; Bergens, S. H. J. Am. Chem. Soc. 2008, 130, 11979.
  (c) Takebayashi, S.; Dabral, N.; Miskolzie, M.; Bergens, S. H. J. Am. Chem. Soc. 2011, 133, 9666.
  (d) John, J. M.; Takebayashi, S.; Dabral, N.; Miskolzie, M.; Bergens, S. H. J. Am. Chem. Soc. 2013, 135, 8578.
29. [29]
  Saudan, L. A.; Saudan, C. M.; Debieux, C.; Wyss, P. Angew. Chem., Int. Ed. 2007, 46, 7473. doi: 10.1002/(ISSN)1521-3773
30. [30]
  (a) Han, Z.; Rong, L.; Wu, J.; Zhang, L.; Wang, Z.; Ding, K. Angew. Chem., Int. Ed. 2012, 51, 13041.
  (b) Zhao, B.; Han, Z.; Ding, K. Angew. Chem., Int. Ed. 2013, 52, 4744.
31. [31]
  Li, W.; Xie, J.; Yuan, M.; Zhou, Q. Green Chem. 2014, 16, 4081. doi: 10.1039/C4GC00835A
32. [32]
  Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. Angew. Chem., Int. Ed. 2006, 45, 1113. doi: 10.1002/(ISSN)1521-3773
33. [33]
  (a) Sun, Y.; Koehler, C.; Tan, R.; Annibale, V. T.; Song, D. Chem. Commun. 2011, 47, 8349.
  (b) Yang, X. ACS Catal. 2012, 2, 964.
34. [34]
  (a) He, Z.; Lin, H.; He, P.; Yuan, Y. J. Catal. 2011, 277, 54.
  (b) Wang, Y.; Duan, X.; Zheng, J.; Lin, H.; Yuan, Y.; Ariga, H.; Takakusagi, S.; Asakura, K. Catal. Sci. Technol. 2012, 2, 1637.
  (c) Huang, Y.; Ariga, H.; Zheng, X.; Duan, X.; Takakusagi, S.; Asakura, K.; Yuan, Y. J. Catal. 2013, 307, 74.
  (d) Zheng, J.; Lin, H.; Wang, Y.; Zheng, X.; Duan, X.; Yuan, Y. J. Catal. 2013, 297, 110.
  (e) Zheng, X.; Lin, H.; Zheng, J.; Duan, X.; Yuan, Y. ACS Catal. 2013, 3, 2738.
  (f) Li, M.; Ye, L.; Zheng, J.; Fang, H.; Kroner, A.; Yuan, Y.; Tsang, S. C. E. Chem. Commun. 2016, 52, 2569.
  (g) Li, M.; Zheng, J.; Qu, J.; Liao, F.; Raine, E.; Kuo, W. C. H.; Su, S. S.; Po, P.; Yuan, Y.; Tsang, S. C. E. Sci. Rep. 2016, 6, 20527.
  (h) Zheng, J.; Duan, X.; Lin, H.; Gu, Z.; Fang, H.; Li, J.; Yuan, Y. Nanoscale 2016, 8, 5959.
35. [35]
  Fang, X.; Zhang, C.; Chen, J.; Zhu, H.; Yuan, Y. RSC Adv. 2016, 6, 45512. doi: 10.1039/C6RA00320F
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