Citation: Bi Siwei, Liu Peng, Ling Baoping, Yuan Xiangai, Jiang Yuanye. Mechanism of N-to-S acyl transfer of N-(2-hydroxybenzyl) cysteine derivatives and origin of phenol acceleration effect[J]. Chinese Chemical Letters, ;2018, 29(8): 1264-1268. doi: 10.1016/j.cclet.2017.11.043 shu

Mechanism of N-to-S acyl transfer of N-(2-hydroxybenzyl) cysteine derivatives and origin of phenol acceleration effect

School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China

Corresponding author: Bi Siwei, siweibi@126.com Jiang Yuanye, qfnu_yuanyejiang@163.com
Received Date: 31 August 2017
Revised Date: 20 November 2017
Accepted Date: 30 November 2017
Available Online: 6 August 2017

Figures(6)

N-(2-Hydroxybenzyl) cysteine derivatives were recently disclosed to be efficient crypto-thioesters for native chemical ligation (NCL). To elucidate the mechanism of the relevant N-to-S acyl transfer process as well as the origin of the acceleration effect of the phenol substitutes, a density functional theory (DFT) study was performed. It was found that the N-to-S acyl transfer of N-(2-hydroxybenzyl) cysteine derivatives involve four major steps:concerted nucleophilic addition of thiolate/proton transfer, inversion of an amine moiety, water-assisted proton transfer and C-N bond cleavage. The phenol substitutes promote the nucleophilic addition of thiolate by protonating the carbonyl oxygen atom synergistically and the proton transfer from hydroxyl to amide nitrogen atom is the rate-determining step of the N-to-S acyl transfer. By contrast, changing the phenolic hydroxyl to methoxyl was found to significantly slow down the nucleophilic addition of thiolate and thus hinders the N-to-S acyl transfer overall. These computational results are consistent with the observation of previously reported control experiments, by which our proposed mechanism is further validated.
- Native chemical ligation,
- Acyl transfer,
- Density functional theory,
- Phenol,
- Proton transfer
1. [1]
  S.B.H. Kent, Chem. Soc. Rev. 38 (2009) 338-351. doi: 10.1039/B700141J
2. [2]
  M. Pan, S. Gao, Y. Zheng, et al., J. Am. Chem. Soc. 138 (2016) 7429-7435. doi: 10.1021/jacs.6b04031
3. [3]
  J. Binschik, H.D. Mootz, Angew. Chem. Int. Ed. 52 (2013) 4260-4264. doi: 10.1002/anie.201208863
4. [4]
  Z. Wang, W. Xu, L. Liu, T.F. Zhu, Nat. Chem. 8 (2016) 698-704. doi: 10.1038/nchem.2517
5. [5]
  A.M. Levinson, J.H. McGee, A.G. Roberts, et al., J. Am. Chem. Soc. 139 (2017) 7632-7639. doi: 10.1021/jacs.7b02988
6. [6]
  J.M. Chalker, Chem. Biol. Drug Des. 81 (2013) 122-135. doi: 10.1111/cbdd.2012.81.issue-1
7. [7]
  S. Liu, B.L. Pentelute, S.B.H. Kent, Angew. Chem. Int. Ed. 51 (2012) 993-999. doi: 10.1002/anie.v51.4
8. [8]
  S. Shang, Z. Tan, S.J. Danishefsky, Proc. Natl. Acad. Sci. U. S. A. 108 (2011) 5986-5989. doi: 10.1073/pnas.1103118108
9. [9]
  I. Sakamoto, K. Tezuka, K. Fukae, et al., J. Am. Chem. Soc.134 (2012) 5428-5431. doi: 10.1021/ja2109079
10. [10]
  P.E. Dawson, T.W. Muir, I. Clark-Lewis, S.B. Kent, Science 266 (1994) 776-779. doi: 10.1126/science.7973629
11. [11]
  Y.C. Huang, G.M. Fang, L. Liu, Natl. Sci. Rev. 3 (2016) 107-116. doi: 10.1093/nsr/nwv072
12. [12]
  S. Bondalapati, M. Jbara, A. Brik, Nat. Chem. 8 (2016) 407-418. doi: 10.1038/nchem.2476
13. [13]
  O. Koniev, A. Wagner, Chem. Soc. Rev. 44 (2015) 5495-5551. doi: 10.1039/C5CS00048C
14. [14]
  H. Li, S. Dong, Sci. China Chem. 60 (2017) 201-213.
15. [15]
  J.B. Blanco-Canosa, P.E. Dawson, Angew. Chem. Int. Ed. 47 (2008) 6851-6855. doi: 10.1002/anie.v47:36
16. [16]
  J.B. Blanco-Canosa, B. Nardone, F. Albericio, P.E. Dawson, J. Am. Chem. Soc. 137 (2015) 7197-7209. doi: 10.1021/jacs.5b03504
17. [17]
  J.X. Wang, G.M. Fang, Y. He, et al., Angew. Chem. Int. Ed. 54 (2015) 2194-2198. doi: 10.1002/anie.201408078
18. [18]
  G.M. Fang, Y.M. Li, F. Shen, et al., Angew. Chem. Int. Ed. 50 (2011) 7645-7649. doi: 10.1002/anie.201100996
19. [19]
  G.M. Fang, J.X. Wang, L. Liu, Angew. Chem. Int. Ed. 51 (2012) 10347-10350. doi: 10.1002/anie.201203843
20. [20]
  T. Kawakami, Top. Curr. Chem. 362 (2015) 107-135.
21. [21]
  J.S. Zheng, H.N. Chang, F.L. Wang, L. Liu, J. Am. Chem. Soc. 133 (2011) 11080-11083. doi: 10.1021/ja204088a
22. [22]
  L. Raibaut, M. Cargoët, N. Ollivier, et al., Chem. Sci. 7 (2016) 2657-2665. doi: 10.1039/C5SC03459K
23. [23]
  S.L. Pira, O. El Mahdi, L. Raibaut, et al., Org. Biomol. Chem.14 (2016) 7211-7216. doi: 10.1039/C6OB01079B
24. [24]
  C. Rao, C.F. Liu, Org. Biomol. Chem. 15 (2017) 2491-2496. doi: 10.1039/C7OB00103G
25. [25]
  H.E. Elashal, Y.E. Sim, M. Raj, Chem. Sci. 8 (2017) 117-123. doi: 10.1039/C6SC02162J
26. [26]
  S. Tsuda, M. Mochizuki, K. Sakamoto, et al., Org. Lett. 18 (2016) 5940-5943. doi: 10.1021/acs.orglett.6b03055
27. [27]
  V.P. Terrier, H. Adihou, M. Arnould, A.F. Delmas, V. Aucagne, Chem. Sci. 7 (2016) 339-345. doi: 10.1039/C5SC02630J
28. [28]
  D. Lelievre, V.P. Terrier, A.F. Delmas, V. Aucagne, Org. Lett. 18 (2016) 920-923. doi: 10.1021/acs.orglett.5b03612
29. [29]
  V.P. Terrier, A.F. Delmas, V. Aucagne, Org. Biomol. Chem. 15 (2017) 316-319. doi: 10.1039/C6OB02546C
30. [30]
  S.B. Pollock, S.B.H. Kent, Chem. Commun. 47 (2011) 2342-2344. doi: 10.1039/C0CC04120C
31. [31]
  C. Wang, Q.X. Guo, Y. Fu, Chem.-Asian J. 6 (2011) 1241-1251. doi: 10.1002/asia.201000760
32. [32]
  C. Wang, L. Liu, Chin. J. Chem. 30 (2012) 1974-1979. doi: 10.1002/cjoc.201200337
33. [33]
  C. Wang, Q.X. Guo, Sci. China Chem. 55 (2012) 2075-2080. doi: 10.1007/s11426-012-4711-x
34. [34]
  Q. Zhang, H.Z. Yu, J. Shi, Acta Phys. Chim. Sin. 29 (2013) 2321-2331.
35. [35]
  X.H. Sun, H.Z. Yu, M.M. Yang, Y.M. Yang, Z.M. Dang, J. Phys. Org. Chem. 28 (2015) 586-590. doi: 10.1002/poc.v28.9
36. [36]
  X.H. Sun, H.Z. Yu, S.Q. Pei, Z.M. Dang, Chin. Chem. Lett. 26 (2015) 1259-1264. doi: 10.1016/j.cclet.2015.07.003
37. [37]
  M.I. Ali Shah, Z.Y. Xu, L. Liu, Y.Y. Jiang, J. Shi, RSC Adv. 6 (2016) 68312-68321. doi: 10.1039/C6RA13793H
38. [38]
  Y.Y. Jiang, C. Wang, Y. Liang, et al., J. Org. Chem. 82 (2017) 1064-1072. doi: 10.1021/acs.joc.6b02642
39. [39]
  Y.Y. Jiang, L. Zhu, X. Man, Y. Liang, S. Bi, Tetrahedron 73 (2017) 4380-4386. doi: 10.1016/j.tet.2017.05.099
40. [40]
  Y. Zhao, D.G. Truhlar, Theor. Chem. Acc. 120 (2008) 215-241. doi: 10.1007/s00214-007-0310-x
41. [41]
  A.V. Marenich, C.J. Cramer, D.G. Truhlar, J. Phys. Chem. B 113 (2009) 6378-6396. doi: 10.1021/jp810292n
42. [42]
  F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 7 (2005) 3297-3305. doi: 10.1039/b508541a
43. [43]
  U.T. Rüegg, J. Rudinger, Methods Enzymol. 47 (1977) 111-116. doi: 10.1016/0076-6879(77)47012-5
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