Citation: Yue Ji, Mu-Wang Chen, Lei Shi, Yong-Gui Zhou. Highly selective partial dehydrogenation of tetrahydroisoquinolines using modified Pd/C[J]. Chinese Journal of Catalysis, ;2015, 36(1): 33-39. doi: 10.1016/S1872-2067(14)60243-6 shu

Highly selective partial dehydrogenation of tetrahydroisoquinolines using modified Pd/C

Yue Ji ^a ,
Mu-Wang Chen ^a ,
Lei Shi ^a,b,, ,
Yong-Gui Zhou ^a,,

1.
a Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;

Corresponding author: Lei Shi, Yong-Gui Zhou,
Received Date: 1 October 2014
Available Online: 3 November 2014
Fund Project: 国家自然科学基金(21202162) (21202162) 大连理工大学精细化工国家重点实验室开放课题基金(KF1110). (KF1110)

A highly selective procedure has been developed for the partial dehydrogenation of 1-substituted-1,2,3,4-tetrahydroisoquinolines over K₃PO₄×3H₂O-modified Pd/C catalyst. This new method provides facile, atom-economical and environmentally friendly access to 1-substituted-3,4-dihydroisoquinolines without the need for stoichiometric amounts of harmful oxidants. The use of standard Pd/C as a catalyst for this process gave poor chemoselectivity. Pleasingly, the use of a K₃PO₄×3H₂O-modified Pd/C catalyst promoted the partial dehydrogenation of 1-substituted-1,2,3,4-tetrahydroisoquinolines with excellent chemoselectivity by suppressing further dehydroaromatization. Furthermore, conducting the reaction under an atmosphere of oxygen led to further improvements in the chemoselectivity of the dehydrogenation, with the ratio of imine to isoquinoline reaching up to 32/1. The heterogenous Pd/C catalyst could also be recycled and reused at least three times with excellent conversion and chemoselectivity, demonstrating the significantly practical potential of this methodology.
- Palladium on carbon,
- Partial dehydrogenation,
- Tetrahydroisoquinoline,
- Imine,
- Dehydroaromatization
1. [1]
  [1] Orito K, Hatakeyama T, Takeo M, Uchiito S, Tokuda M, Suginome H. Tetrahedron, 1998, 54: 8403
2. [2]
  [2] Ajzert K I, Takács K. Liebigs Ann Chem, 1987: 1061
3. [3]
  [3] Khatri P K, Jain S L, Sivakumar K L N, Sain B. Org Biomol Chem, 2011, 9: 3370
4. [4]
  [4] Yao W B, Zhang Y X, Jia X Q, Huang Z. Angew Chem Int Ed, 2014, 53: 1390
5. [5]
  [5] Choi H, Doyle M P. Chem Commun, 2007: 745
6. [6]
  [6] Goti A, Romani M. Tetrahedron Lett, 1994, 35: 6567
7. [7]
  [7] Kamal A, Devaiah V, Reddy K L, Shankaraiah N. Adv Synth Catal, 2006, 348: 249
8. [8]
  [8] Chen Y, Crockett R D, Wang X, Larsen R D, Cui S, Faul M M. Synlett, 2013, 24: 301
9. [9]
  [9] Aoyama T, Sonoda N, Yamauchi M, Toriyama K, Anzai M, Ando A, Shioiri T. Synlett, 1998, 1: 35
10. [10]
  [10] Huang B, Tian H W, Lin S S, Xie M H, Yu X C, Xu Q. Tetrahedron Lett, 2013, 54: 2861
11. [11]
  [11] Reyes-Sánchez A, Cañavera-Buelvas F, Barrios-Francisco R, Cifuentes-Vaca O L, Flores-Alamo M, García J J. Organometallics, 2011, 30: 3340
12. [12]
  [12] Bolchi C, Pallavicini M, Fumagalli L, Straniero V, Valoti E. Org Process Res Dev, 2013, 17: 432
13. [13]
  [13] Scully F E Jr, Schlager J J. Heterocycles, 1982, 19: 653
14. [14]
  [14] Choi J, MacArthur A H R, Brookhart M, Goldman A S. Chem Rev, 2011, 111: 1761
15. [15]
  [15] Esswein A J, Nocera D G. Chem Rev, 2007, 107: 4022
16. [16]
  [16] Zhang W, Ma H, Zhou L P, Miao H, Xu J. Chin J Catal (张伟, 马红, 周利鹏, 苗虹, 徐杰. 催化学报), 2009, 30: 86
17. [17]
  [17] Li C G, Miao C X, Nie Y Y, Yue Y H, Gu S Y, Yang W M, Hua W M, Gao Z. Chin J Catal (李春光, 缪长喜, 聂颖颖, 乐英红, 顾松园, 杨为民, 华伟明, 高滋. 催化学报), 2010, 31: 993
18. [18]
  [18] Ye X N, Hua W M, Yue Y H, Miao C X, Xie Z K, Gao Z. Chin J Catal (叶兴南, 华伟明, 乐英红, 缪长喜, 谢在库, 高滋. 催化学报), 2004, 25: 581
19. [19]
  [19] Jin M, Cheng Z M, Jiang X X, Gao Y L, Fang X C. Chin J Catal (晋梅, 程振民, 江晓霞, 高玉兰, 方向晨. 催化学报), 2010, 31: 1177
20. [20]
  [20] Dobereiner G E, Crabtree R H. Chem Rev, 2010, 110: 681
21. [21]
  [21] Schümperli M T, Hammond C, Hermans I. ACS Catal, 2012, 2:1108
22. [22]
  [22] Largeron M. Eur J Org Chem, 2013: 5225
23. [23]
  [23] Patil R D, Adimurthy S. Asian J Org Chem, 2013, 2: 726
24. [24]
  [24] Angelici R J. Catal Sci Technol, 2013, 3: 279
25. [25]
  [25] Turner N J. Chem Rev, 2011, 111: 4073
26. [26]
  [26] Li Z C, Chen C H, Zhan E S, Ta N, Shen W J. Catal Commun, 2014, 51: 58
27. [27]
  [27] Li Z C, Chen C H, Zhan E S, Ta N, Li Y, Shen W J. Chem Commun, 2014, 50: 4469
28. [28]
  [28] Li Z C, Li Y, Zhan E S, Ta N, Shen W J. J Mater Chem A, 2013, 1: 15370
29. [29]
  [29] Shi Q J, Liu N, Liang Y. Chin J Catal (石秋杰, 刘宁, 梁义. 催化学报), 2007, 28: 57
30. [30]
  [30] Chen J, Zhang Q H, Fang W H, Wang Y, Wan H L. Chin J Catal (陈静, 张庆红, 方文浩, 王野, 万惠霖. 催化学报), 2010, 31: 1061
31. [31]
  [31] Wang F, Shi R J, Liu Z Q, Shang P J, Pang X Y, Shen S, Feng Z C, Li C, Shen W J. ACS Catal, 2013, 3: 890
32. [32]
  [32] Adkins H, Lundsted L G. J Am Chem Soc, 1949, 71: 2964
33. [33]
  [33] Angelici R J. J Organomet Chem, 2008, 693: 847
34. [34]
  [34] Jin X K, Liu Y X, Lu Q Q, Yang D Y, Sun J K, Qin S S, Zhang J W, Shen J X, Chu C H, Liu R H. Org Biomol Chem, 2013, 11: 3776
35. [35]
  [35] Gu X Q, Chen W, Morales-Morales D, Jensen C M. J Mol Catal A, 2002, 189: 119
36. [36]
  [36] Lu S M, Wang Y Q, Han X W, Zhou Y G. Chin J Catal (卢胜梅, 汪游清, 韩秀文, 周永贵. 催化学报), 2005, 26: 287
37. [37]
  [37] Wang D W, Wang X B, Wang D S, Lu S M, Zhou Y G, Li Y X. J Org Chem, 2009, 74: 2780
38. [38]
  [38] Yamaguchi R, Ikeda C, Takahashi Y, Fujita K I. J Am Chem Soc, 2009, 131: 8410
39. [39]
  [39] Wu J J, Talwar D, Johnston S, Yan M, Xiao J L. Angew Chem Int Ed, 2013, 52: 6983
40. [40]
  [40] Fujita K I, Tanaka Y, Kobayashi M, Yamaguchi R. J Am Chem Soc, 2014, 136: 4829
41. [41]
  [41] Yi C S, Lee D W. Organometallics, 2009, 28: 947
42. [42]
  [42] Wendlandt A E, Stahl S S. J Am Chem Soc, 2014, 136: 11910
43. [43]
  [43] Hara T, Mori K, Mizugaki T, Ebitani K, Kaneda K. Tetrahedron Lett, 2003, 44: 6207
44. [44]
  [44] Dean D, Davis B, Jessop P G. New J Chem, 2011, 35: 417
45. [45]
  [45] Chakraborty S, Brennessel W W, Jones W D. J Am Chem Soc, 2014, 136: 8564
46. [46]
  [46] Luca O R, Huang D L, Takase M K, Crabtree R H. New J Chem, 2013, 37: 3402
47. [47]
  [47] Zhang D, Wu L Z, Zhou L, Han X, Yang Q Z, Zhang L P, Tung C H. J Am Chem Soc, 2004, 126: 3440
48. [48]
  [48] Li H, Jiang J, Lu G, Huang F, Wang Z X. Organometallics, 2011, 30: 3131
49. [49]
  [49] Zhang X B, Xi Z. Phys Chem Chem Phys, 2011, 13: 3997
50. [50]
  [50] Wendlandt A E, Stahl S S. J Am Chem Soc, 2014, 136: 506
51. [51]
  [51] Ghislieri D, Green A P, Pontini M, Willies S C, Rowles I, Frank A, Grogan G, Turner N J. J Am Chem Soc, 2013, 135: 10863
52. [52]
  [52] Sonobe T, Oisaki K, Kanai M. Chem Sci, 2012, 3: 3249
53. [53]
  [53] Ruži M, Pečavar A, Prudič D, Kralj D, Scriban C, Antonio Z G. Org Process Res Dev, 2012, 16: 1293
54. [54]
  [54] Chang M X, Li W, Zhang X M. Angew Chem Int Ed, 2011, 50: 10679
55. [55]
  [55] Dong J, Shi X X, Yan J J, Xing J, Zhang Q, Xiao S. Eur J Org Chem, 2010: 698
56. [56]
  [56] Berhal F, Wu Z, Zhang Z G, Ayad T, Ratovelomanana-Vidal V. Org Lett, 2012, 14: 3308
57. [57]
  [57] Romines K R, Freeman G A, Schaller L T, Cowan J R, Gonzales S S, Tidwell J H, Andrews III C W, Stammers D K, Hazen R J, Ferris R G, Short S A, Chan J H, Boone L R. J Med Chem, 2006, 49: 727
58. [58]
  [58] Dong J, Shi X X, Xing J, Yan J J. Synth Commun, 2012, 42: 2806
59. [59]
  [59] Jin Q R, Jia G Q, Zhang Y M, Li C. Catal Sci Technol, 2014, 4: 464
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