Citation: Ruixue Liu, Xiaobing Ding, Qiwei Lang, Gen-Qiang Chen, Xumu Zhang. Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation[J]. Chinese Chemical Letters, ;2025, 36(3): 110037. doi: 10.1016/j.cclet.2024.110037 shu

Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation

Ruixue Liu ^a ,
Xiaobing Ding ^a ,
Qiwei Lang ^{a, *,} ,
Gen-Qiang Chen ^{a, b, *,} ,
Xumu Zhang ^{a, c, *,}

a.
Department of Chemistry, Medi-Pingshan and Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518000, China
b.
Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen 518000, China
c.
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, China

langqw@sustech.edu.cn

chengq@sustech.edu.cn

zhangxm@sustech.edu.cn

Received Date: 12 March 2024
Revised Date: 10 May 2024
Accepted Date: 21 May 2024
Available Online: 22 May 2024

Figures(5)

The dynamic kinetic resolution (DKR) process remains a highly efficacious approach for constructing chiral amino alcohols via the catalytic asymmetric hydrogenation of α-amino ketones. We report herein a highly efficient and enantioselective anti-selective dynamic kinetic asymmetric hydrogenation of α-amino ketones catalyzed by Ir-(S)-f-phamidol system, providing various chiral amino alcohols and chiral oxazolidin-2-ones divergently with high diastereo- and enantioselectivity (up to 99% yield, up to 99% ee and up to 99:1 dr). In addition, the reaction could be performed on the gram-scale, and the resulting chiral amino alcohols are key intermediates of norephedrine and metaraminol.
- Asymmetric hydrogenation,
- α-Amino ketone,
- f-Phamidol,
- Iridium-catalysed,
- Divergent synthesis
1. [1]
  S.C. Bergmeier, Tetrahedron 56 (2000) 2561–2576. doi: 10.1016/S0040-4020(00)00149-6
2. [2]
  T.J. Donohoe, C.K. Callens, A. Flores, A.R. Lacy, A.H. Rathi, Chem. Eur. J. 17 (2011) 58–76. doi: 10.1002/chem.201002323
3. [3]
  E. Freyne, A. Raeymaekers, M. Venet, G. Sanz, J.V. Wauwe, Bioorg. Med. Chem. Lett. 8 (1998) 267–272. doi: 10.1016/S0960-894X(98)00004-3
4. [4]
  P.E. Goss, A. Oza, R. Goel, et al., Breast Cancer Res. Treat. 59 (2000) 55–68. doi: 10.1023/A:1006320122711
5. [5]
  A.B. Weinstein, D.P. Schuman, Z.X. Tan, S.S. Stahl, Angew. Chem. Int. Ed. 52 (2013) 11867–11870. doi: 10.1002/anie.201305926
6. [6]
  J. Wang, A. Shy, D. Wu, et al., J. Med. Chem. 62 (2019) 10245–10257. doi: 10.1021/acs.jmedchem.9b01210
7. [7]
  N.F. Albertson, F.C. Mckay, H.E. Lape, et al., J. Med. Chem. 13 (1970) 132. doi: 10.1021/jm00295a033
8. [8]
  J.Y.L. Chung, J.P. Scott, C. Anderson, et al., Org. Process Res. Dev. 19 (2015) 1760–1768. doi: 10.1021/acs.oprd.5b00267
9. [9]
  T. Biftu, R. Sinha-Roy, P. Chen, et al., J. Med. Chem. 57 (2014) 3205–3212. doi: 10.1021/jm401992e
10. [10]
  Smith, J. Med. Microbiol. 6 (1973) 347–350. doi: 10.1099/00222615-6-3-347
11. [11]
  T. Komuro, Y. Nakajima, J. Takaya, H. Hashimoto, Coord. Chem. Rev. 473 (2022) 214837. doi: 10.1016/j.ccr.2022.214837
12. [12]
  H. Ibrahim, M.D. Bala, H.B. Friedrich, Coord. Chem. Rev. 469 (2022) 214652. doi: 10.1016/j.ccr.2022.214652
13. [13]
  F. Gonzalez-Lopez de Turiso, D. Sun, Y. Rew, et al., Br. J. Pharmacol. 89 (1986) 219–228. doi: 10.1111/j.1476-5381.1986.tb11138.x
14. [14]
  F. Wang, T. Yang, T. Wu, et al., J. Am. Chem. Soc. 143 (2021) 2477–2483. doi: 10.1021/jacs.0c13273
15. [15]
  J.M. Takacs, M.R. Jaber, A.S. Vellekoop, J. Org. Chem. 63 (1998) 2742–2748. doi: 10.1021/jo9720804
16. [16]
  M.E. Dyen, D. Swern, Chem. Rev. 67 (1967) 197–246. doi: 10.1021/cr60246a003
17. [17]
  P. Tang, H. Wang, W. Zhang, F.E. Chen, Green Synth. Catal. 1 (2020) 26–41. doi: 10.1016/j.gresc.2020.05.006
18. [18]
  R. Noyori, T. Ikeda, T. Ohkuma, et al., J. Am. Chem. Soc. 111 (1989) 8291–8327. doi: 10.1021/ja00203a047
19. [19]
  R. Noyori, T. Ohkuma, Angew. Chem. Int. Ed. 40 (2001) 40–73. doi: 10.1002/1521-3773(20010105)40:1<40::AID-ANIE40>3.0.CO;2-5
20. [20]
  S. Liu, J.H. Xie, L.X. Wang, Q.L. Zhou, Angew. Chem. Int. Ed. 46 (2007) 7506–7508. doi: 10.1002/anie.200702491
21. [21]
  J.H. Xie, Z.T. Zhou, W.L. Kong, Q.L. Zhou, J. Am. Chem. Soc. 129 (2007) 1868–1869. doi: 10.1021/ja0680109
22. [22]
  F. Wang, Z. Zhang, Y. Chen, et al., Nat. Commun. 13 (2022) 7794. doi: 10.1038/s41467-022-35124-5
23. [23]
  K. Akira, T. Masami, K. Hitoshi, N. Ken-ichi, Tetrahedron Lett. 36 (1995) 6251–6252. doi: 10.1016/0040-4039(95)01236-B
24. [24]
  A. Lei, S. Wu, M. He, X. Zhang, J. Am. Chem. Soc. 126 (2004) 1626–1627. doi: 10.1021/ja039153n
25. [25]
  T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 117 (1995) 2675–2676. doi: 10.1021/ja00114a043
26. [26]
  T. Ohkuma, H. Ooka, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 117 (1995) 10417–10418. doi: 10.1021/ja00146a041
27. [27]
  R. Noyori, T. Okhuma, Angew. Chem., Int. Ed. 40 (2001) 40–73. doi: 10.1002/1521-3773(20010105)40:1<40::AID-ANIE40>3.0.CO;2-5
28. [28]
  Y.M. Cui, L.L. Wang, F.Y. Kwong, W. Sun, Chin. Chem. Lett. 21 (2010) 1403–1406. doi: 10.1016/j.cclet.2010.05.027
29. [29]
  S. Liu, J.H. Xie, W. Li, et al., Org. Lett. 11 (2009) 4994–4997. doi: 10.1021/ol901605a
30. [30]
  J.H. Xie, S. Liu, W.L. Kong, et al., J. Am. Chem. Soc. 131 (2009) 4222–4223. doi: 10.1021/ja901058u
31. [31]
  Y.X. Ding, Z.H. Zhu, H. Wang, C.B. Yu, Y.G. Zhou, Sci. China Chem. 64 (2020) 232–237. doi: 10.1109/iv47402.2020.9304677
32. [32]
  M.L. Ma, C.H. Ren, Y.J. Lv, H. Chen, X.J. Li, Chin. Chem. Lett. 22 (2011) 155–158. doi: 10.1016/j.cclet.2010.09.025
33. [33]
  W. Wu, C. You, C. Yin, Y. Liu, X.Q. Dong, X. Zhang, Org. Lett. 19 (2017) 2548–2551. doi: 10.1021/acs.orglett.7b00844
34. [34]
  Y. Hu, W. Wu, X.Q. Dong, X. Zhang, Org. Chem. Front. 4 (2017) 1499–1502. doi: 10.1039/C7QO00237H
35. [35]
  B. He, J. Song, C. Yin, G.Q. Chen, X. Zhang, Org. Chem. Front. 9 (2022) 6247–6251. doi: 10.1039/d2qo01121b
36. [36]
  J.H. Xie, X.Y. Liu, J.B. Xie, L.X. Wang, Q.L. Zhou, Angew. Chem. Int. Ed. 50 (2011) 7329–7332. doi: 10.1002/anie.201102710
37. [37]
  X.H. Yang, K. Wang, S.F. Zhu, J.H. Xie, Q.L. Zhou, J. Am. Chem. Soc. 136 (2014) 17426–17429. doi: 10.1021/ja510990v
38. [38]
  Q.Q. Zhang, J.H. Xie, X.H. Yang, J.B. Xie, Q.L. Zhou, Org. Lett. 14 (2012) 6158–6161. doi: 10.1021/ol302842h
39. [39]
  Q.L. Zhou, J.H. Xie, M.L. Yuan, X.H. Yang, Synthesis 46 (2014) 2910–2916. doi: 10.1055/s-0034-1378891
40. [40]
  X.S. Gu, N. Yu, X.H. Yang, et al., Org. Lett. 21 (2019) 4111–4115. doi: 10.1021/acs.orglett.9b01290
41. [41]
  W. Wu, S. Liu, M. Duan, et al., Org. Lett. 18 (2016) 2938–2941. doi: 10.1021/acs.orglett.6b01290
42. [42]
  J. Wang, P.L. Shao, X. Lin, et al., Angew. Chem. Int. Ed. 59 (2020) 18166–18171. doi: 10.1002/anie.202006661
43. [43]
  Y. Zheng, X. Zhang, R. Zhang, B. Ma, Green Synth. Catal. 2 (2021) 393–396. doi: 10.1016/j.gresc.2021.09.002
44. [44]
  J. Yu, F. Huang, W. Fang, et al., Green Synth. Catal. 3 (2022) 175–178. doi: 10.1016/j.gresc.2022.03.004
45. [45]
  J. Yu, J. Long, Y. Yang, et al., Org. Lett. 19 (2017) 690–693. doi: 10.1021/acs.orglett.6b03862
46. [46]
  G. Gu, T. Yang, J. Lu, et al., Org. Chem. Front. 5 (2018) 1209–1212. doi: 10.1039/c8qo00047f
47. [47]
  Q. Gong, J. Wen, X. Zhang, Chem. Sci. 10 (2019) 6350–6353. doi: 10.1039/c9sc01769k
48. [48]
  J. Yu, M. Duan, W. Wu, et al., Chem. Eur. J. 23 (2017) 970–975. doi: 10.1002/chem.201604855
49. [49]
  G. Gu, J. Lu, O. Yu, et al., Org. Lett. 20 (2018) 1888–1892. doi: 10.1021/acs.orglett.8b00433
50. [50]
  C. Yin, X.Q. Dong, X. Zhang, Adv. Synth. Catal. 360 (2018) 4319–4324. doi: 10.1002/adsc.201800839
51. [51]
  Z. Liang, T. Yang, G. Gu, L. Dang, X. Zhang, Chin. J. Chem. 36 (2018) 851–856. doi: 10.1002/cjoc.201800129
52. [52]
  B. Seashore-Ludlow, P. Villo, P. Somfai, Chem. Eur. J. 18 (2012) 7219–7223. doi: 10.1002/chem.201103739
53. [53]
  B. Seashore-Ludlow, P. Villo, C. Hacker, P. Somfai, Org. Lett. 12 (2010) 5274–5277. doi: 10.1021/ol102323k
54. [54]
  S.K. Gediya, G.J. Clarkson, M. Wills, J. Org. Chem. 85 (2020) 11309–11330. doi: 10.1021/acs.joc.0c01438
55. [55]
  X. Tan, S. Gao, C. Yang, et al., Sci. China Chem. 66 (2023) 2847–2851. doi: 10.1007/s11426-023-1798-1
56. [56]
  H.K. Lee, S. Kang, E.B. Choi, J. Org. Chem. 77 (2012) 5454–5460. doi: 10.1021/jo300867y
57. [57]
  M. Hemmerling, S. Nilsson, K. Edman, et al., J. Med. Chem. 60 (2017) 8591–8605. doi: 10.1021/acs.jmedchem.7b01215
58. [58]
  G.S. Sarin, S. Vyas, V. Kumar, H. Atkinson, An industrial process for the preparation of pure metaraminol or salts thereof. IN2019-11035205, 2021-03-05.
59. [59]
  C. Yin, Y.F. Jiang, F. Huang, et al., Nat. Commun. 14 (2023) 3718. doi: 10.1038/s41467-023-39375-8
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