Citation: Xin Li, Jia-Min Lu, Bo Li, Chen Zhao, Bei-Bei Yang, Li Li. Chiroptical sensing for remote chiral amines via a C–H activation reaction[J]. Chinese Chemical Letters, ;2025, 36(5): 110310. doi: 10.1016/j.cclet.2024.110310 shu

Chiroptical sensing for remote chiral amines via a C–H activation reaction

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State Key Laboratory of Digestive Health, Beijing Key Laboratory of Active Substances Discovery and Druggability Evaluation, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, China

annaleelin@imm.ac.cn

Received Date: 16 March 2024
Revised Date: 16 July 2024
Accepted Date: 31 July 2024
Available Online: 2 August 2024

Figures(11)

An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)₂, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
- Electronic circular dichroism (ECD),
- Remote chiral amines,
- C–H activation,
- Cyclo-palladium,
- Absolute optical purity
1. [1]
  J. Valentová, L. Lintnerová, N. Miklášová, et al., Int. J. Mol. Sci. 24 (2023) 5679. doi: 10.3390/ijms24065679
2. [2]
  D. Saha, A. Kharbanda, W. Yan, et al., J. Med. Chem. 63 (2020) 441–469. doi: 10.1021/acs.jmedchem.9b00640
3. [3]
  X. Chu, Y. Bu, X. Yang, Front. Oncol. 11 (2021) 785855.
4. [4]
  S. Jang, H. Park, Q.H. Duong, et al., Anal. Chem. 94 (2022) 1441–1446. doi: 10.1021/acs.analchem.1c04834
5. [5]
  G. Pescitelli, Chirality 34 (2022) 333–363. doi: 10.1002/chir.23393
6. [6]
  A. Mándi, T. Kurtán, Nat. Prod. Rep. 36 (2019) 889–918. doi: 10.1039/c9np00002j
7. [7]
  F. Krupp, W. Frey, C. Richert, Angew. Chem. Int. Ed. 59 (2020) 15875–15879. doi: 10.1002/anie.202004992
8. [8]
  M. Chen, C. Qi, Y. Yin. et al., Org. Chem. Front. 9 (2022) 5160–5167. doi: 10.1039/d2qo01073a
9. [9]
  Y. Wu, P. Wang, L. Zheng, et al., Sensor. Actuat. B: Chem. 380 (2023) 133330.
10. [10]
  M.-S. Seo, K.H. Jung, K. Kim, et al., Biomed. Pharmacother. 152 (2022) 113241.
11. [11]
  P. Linnane, N. Magnus, P. Magnus, Nature 385 (1997) 799–801.
12. [12]
  H.Q. Shen, B. Wu, H.P. Xie, et al., Org. Lett. 21 (2019) 2712–2717. doi: 10.1021/acs.orglett.9b00687
13. [13]
  S.A. Shyshkanov, N.V. Orlov, Chem. Eur. J. 22 (2016) 15458–15467. doi: 10.1002/chem.201602884
14. [14]
  M. Tanasova, M. Anyika, B. Borhan, Angew. Chem. Int. Ed. 54 (2015) 4274–4278. doi: 10.1002/anie.201410371
15. [15]
  L.A. Joyce, J.W. Canary, E.V. Anslyn, Chemistry (Easton) 18 (2012) 8064–8069. doi: 10.1002/chem.201103592
16. [16]
  L.A. Joyce, M.S. Maynor, J.M. Dragna, et al., J. Am. Chem. Soc. 133 (2011) 13746–13752. doi: 10.1021/ja205775g
17. [17]
  M.B. Minus, A.L. Featherston, S. Choi, et al., Chem 5 (2019) 3196–3206.
18. [18]
  J. Yang, X.M. Zhang, F.M. Zhang, et al., Angew. Chem. Int. Ed. 59 (2020) 8471–8475. doi: 10.1002/anie.202001100
19. [19]
  Z.K. Xue, N.K. Fu, S.Z. Luo, Chin. Chem. Lett. 28 (2017) 1083–1086.
20. [20]
  L. Næsborg, V. Corti, L.A. Leth, et al., Angew. Chem. Int. Ed.57 (2018) 1606–1610. doi: 10.1002/anie.201711944
21. [21]
  B. Li, J. Zhang, L. Li, et al., Chem. Sci. 12 (2020) 2504–2508. doi: 10.1021/acs.joc.9b03204
22. [22]
  S.L. Pilicer, C. Wolf, J. Org. Chem. 85 (2020) 11560–11565. doi: 10.1021/acs.joc.0c01515
23. [23]
  A. Sripada, F.Y. Thanzeel, C. Wolf, Chem 8 (2022) 1734–1749.
24. [24]
  J. Zhang, B. Yang, Y. Yang, et al., Ultrason. Sonochem. 86 (2022) 106007.
25. [25]
  K. Ngamdee, W. Ngeontae, Sensor. Actuat. B: Chem. 274 (2018) 402–411.
26. [26]
  A. Chen, Y. Zhong, X. Yin, et al., Sensor. Actuat. B: Chem. 393 (2023) 134262.
27. [27]
  W. Ali, G. Prakash, D. Maiti, Chem. Sci. 12 (2021) 2735–2759. doi: 10.1039/d0sc05555g
28. [28]
  G. Liao, T. Zhang, Z.K. Lin, et al., Angew. Chem. Int. Ed. 59 (2020) 19773–19786. doi: 10.1002/anie.202008437
29. [29]
  M. Zhang, S. Zhong, Y. Peng, et al., Org. Chem. Front. 8 (2021) 133–168. doi: 10.1039/d0qo00988a
30. [30]
  Y. Han, B. Shi, Acta Chim. Sinica 81 (2023) 1522–1540. doi: 10.6023/a23070336
31. [31]
  B. Liu, A.M. Romine, C.Z. Rubel, et al., Chem. Rev. 121 (2021) 14957–15074. doi: 10.1021/acs.chemrev.1c00519
32. [32]
  Q. Zhang, B. Shi, Acc. Chem. Res. 54 (2021) 2750–2763. doi: 10.1021/acs.accounts.1c00168
33. [33]
  J. Zhang, B. Lu, Z. Ge, et al., Org. Lett. 24 (2022) 8423–8428. doi: 10.1021/acs.orglett.2c03543
34. [34]
  M. Zheng, J. Zhou, F. Fang, et al., Org. Chem. Front. 10 (2023) 62–67. doi: 10.1039/d2qo01529c
35. [35]
  K.K. Pasunooti, B. Banerjee, T. Yap, et al., Org. Lett. 17 (2015) 6094–6097. doi: 10.1021/acs.orglett.5b03118
36. [36]
  K.K. Pasunooti, R. Yang, B. Banerjee, et al., Org. Lett. 18 (2016) 2696–2699. doi: 10.1021/acs.orglett.6b01160
37. [37]
  J.M. Gonzalez, X. Vidal, M.A. Ortuno, et al., J. Am. Chem. Soc. 144 (2022) 21437–21442. doi: 10.1021/jacs.2c09479
38. [38]
  J. Wang, D. Hu, X. Sun, et al., Org. Lett. 25 (2023) 2006–2011. doi: 10.1021/acs.orglett.3c00189
39. [39]
  Q. Li, K. Yan, Y. Zhu, et al., Chin. Chem. Lett. 34 (2023) 108014.
40. [40]
  Y. Peng, Q. He, X. Zhang, et al., Org. Chem. Front. 6 (2019) 3234–3237. doi: 10.1039/c9qo00484j
41. [41]
  J. Frelek, W.J. Szczepek, Tetrahedron: Asymmetr. 10 (1999) 1507–1520.
42. [42]
  A.V. Marenich, C.J. Cramer, D.G. Truhlar, J. Phys. Chem. B 113 (2009) 6378–6396. doi: 10.1021/jp810292n
43. [43]
  T. Lu, F.Y. Chen, J. Comput. Chem. 33 (2012) 580–592. doi: 10.1002/jcc.22885
44. [44]
  T. Bruhn, A. Schaumlöffel, Y. Hemberger, et al., SpecDis Version 1.71, Berlin, Germany, 2017. https://specdis-software.jimdo.com.
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