Citation: Xiao Chang, Zhang Song-Lin. Mechanism for acetic acid-catalyzed ester aminolysis[J]. Chinese Chemical Letters, ;2018, 29(8): 1233-1236. doi: 10.1016/j.cclet.2018.01.003 shu

Mechanism for acetic acid-catalyzed ester aminolysis

Xiao Chang ,
Zhang Song-Lin ^,

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China

Corresponding author: Zhang Song-Lin, slzhang@jiangnan.edu.cn
Received Date: 16 November 2017
Revised Date: 20 December 2017
Accepted Date: 27 December 2017
Available Online: 5 August 2018

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This paper reports a computational study elucidating reaction mechanism for amide bond formation from esters and amines catalyzed by acetic acid. Two optional mechanisms (namely, classic stepwise and concerted acyl substitution mechanisms) have been studied. Calculation results establish the reaction energy profiles of both mechanisms and locate all the intermediates and transition states in both catalytic cycles. Our results propose that the concerted acyl substitution mechanism may be more likely wherein the formation of C-N bond and the cleavage of C-O bond occur concurrently without the need of rehybridization of the carbonyl carbon. This is also consistent with the fact that no significant racemization/epimerization were observed in the amide products when asymmetric esters and/or amines were used as the reactants, because concerted acyl substitution mechanism precludes the intermediacy of tetrahedral adducts and the accompanying generation/elimination of new chiral centers. Further discussion implies that the concerted acyl substitution mechanism may widely occur in related amidation reactions in the presence of different types of coupling reagents.
- Amide bond formation,
- Aminolysis,
- Mechanism,
- Ester,
- Concerted acyl substitution,
- Acid catalyzed amidation
1. [1]
  (a) E. Valeur, M. Bradley, Chem. Soc. Rev. 38 (2009) 606-631
  (b) C. L. Allen, J. M. J. Williams, Chem. Soc. Rev. 40 (2011) 3405
  (c) V. R. Pattabiraman, J. W. Bode, Nature 480 (2011) 471-479
  (d) H. Lundberg, F. Tinnis, N. Selander, H. Adolfsson, Chem. Soc. Rev. 43 (2014) 2714-2742.
2. [2]
  (a) A. El-Faham, F. Albericio, Chem. Rev. 111 (2011) 6557-6602
  (b) J. C. Sheehan, G. P. Hess, J. Am. Chem. Soc. 77 (1955) 1067-1068
  (c) G. Gawne, G. W. Kenner, R. C. Sheppard, J. Am. Chem. Soc. 91 (1969) 5669-5671
  (d) L. A. Carpino, P. Henklein, B. M. Foxman, et al., J. Org. Chem. 66 (2001) 5245-5247.
3. [3]
  (a) J. W. Bode, R. M. Fox, K. D. Baucom, Angew. Chem. Int. Ed. 45 (2006) 1248-1252
  (b) B. Shen, D. M. Makley, J. N. Johnston, Nature 465 (2010) 1027-1032
  (c) W. Wu, Z. Zhang, L. S. Liebeskind, J. Am. Chem. Soc. 133 (2011) 14256-14259
  (d) G. M. Fang, Y. M. Li, F. Shen, et al., Angew. Chem. Int. Ed. 50 (2011) 7645-7649
  (e) J. F. Soulé, H. Miyamura, S. Kobayashi, J. Am. Chem. Soc. 133 (2011) 18550-18553
  (f) A. M. Dumas, G. A. Molander, J. W. Bode, Angew. Chem. Int. Ed. 51 (2012) 5683-5686
  (g) J. X. Wang, G. M. Fang, Y. He, et al., Angew. Chem. Int. Ed. 54 (2015) 2194-2198
  (h) J. Li, M. J. Lear, Y. Kawamoto, et al., Angew. Chem. Int. Ed. 54 (2015) 12986-12990
  (i) H. Noda, J. W. Bode, J. Am. Chem. Soc. 137 (2015) 3958-3966.
4. [4]
  (a) C. G. McPherson, N. Caldwell, C. Jamieson, I. Simpson, A. J. B. Watson, Org. Biomol. Chem. 15 (2017) 3507-3518
  (b) C. Sabot, K. A. Kumar, S. Meunier, C. Mioskowski, Tetrahedron Lett. 48 (2007) 3863-3866
  (c) N. Caldwell, C. Jamieson, I. Simpson, A. J. B. Watson, Chem. Commun. 51 (2015) 9495-9498.
5. [5]
  D.D.S. Sharley, J.M.J. Williams, Chem. Commun. 53(2017) 2020-2023. doi: 10.1039/C6CC09023K
6. [6]
  H. Charville, D.A. Jackson, G. Hodges, A. Whiting, M.R. Wilson, Eur. J. Org. Chem. (2011) 5981-5990.
7. [7]
  (a) T. Krause, S. Baader, B. Erb, L. J. Gooßen, Nat. Commun. 7 (2016) 11732
  (b) L. Hu, S. Xu, Z. Zhao, et al., J. Am. Chem. Soc. 138 (2016) 13135-13138.
8. [8]
  S.L. Zhang, H.X. Wan, Z.Q. Deng, Org. Biomol. Chem. 15(2017) 6367-6374. doi: 10.1039/C7OB01378G
9. [9]
  M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 09, Revision D. 01, Gaussian, Inc., Wallingford, CT, 2013.
10. [10]
  (a) A. D. Becke, J. Chem. Phys. 98 (1993) 5648-5652
  (b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 37 (1988) 785-789.
11. [11]
  M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Compt. Chem. 24(2003) 669-681. doi: 10.1002/jcc.10189
12. [12]
  (a) J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 105 (2005) 2999-3093
  (b) Y. Fu, L. Liu, R. Q. Li, R. Liu, Q. X. Guo, J. Am. Chem. Soc. 126 (2004) 814-822.
13. [13]
  (a) C. Gonzalez, H. B. Schlegel, J. Phys. Chem. 94 (1990) 5523-5527
  (b) K. Fukui, Acc. Chem. Res. 14 (1981) 363-368.
14. [14]
  G.W. Anderson, F. Callahan, J. Am. Chem. Soc. 80(1958) 2902-2903. doi: 10.1021/ja01544a077
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