Citation: Li Zhewei, Wang Qianyue, Pu Min, Yang Zuoyin, Lei Ming. Theoretical Study on Nitrogenous Heterocyclic Assisted Aldimine Condensation[J]. Acta Chimica Sinica, ;2020, 78(5): 437-443. doi: 10.6023/A19110413 shu

Theoretical Study on Nitrogenous Heterocyclic Assisted Aldimine Condensation

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Institute of Computational Chemistry, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Pu Min, pumin@mail.buct.edu.cn Lei Ming, leim@mail.buct.edu.cn
Received Date: 26 November 2019
Available Online: 8 April 2020
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21672018), the State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University) (No. 201811) and the Fundamental Research Funds for the Central Universities (No. XK1802-6)the State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University) 201811the National Natural Science Foundation of China 21672018the Fundamental Research Funds for the Central Universities XK1802-6

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Imines and the intermediate methylamine by the aldimine condensation of primary amines with aldehydes have a potential application in the field of pharmacy, life science, catalysis, material science, etc. In this reaction, the hydrogen transfer in the dehydration step normally prefers the pathway via a water bridge in aqueous solution or a directly dehydration in organic solvent. It is a different mechanism for the aldimine condensation of amine owning neighbouring nitrogenous heterocycle. Herein we investigated the mechanism of aldimine condensation of primary amine containing nitrogenous heterocycle with aldehyde in dichloromethane under acidic conditions using density functional theory (DFT) at ωB97X-D/6-31++G(d, p) level, the calculated results show that compared with specific acid catalysis, the heterocyclic nitrogen with stronger basicity is easier to be protonated than the oxygen of carbonyl group. The whole reaction proceeds two hydrogen transfer steps via nitrogen bridge owning an energy span of 13.08 kcal/mol. The rate-determing step is the second hydrogen transfer step. In each step the heterocyclic nitrogen is a bridge to assist the hydrogen transfer, which could reduce the free energy barrier of the aldimine condensation. It is unfavorable for the reaction pathway via directly hydrogen transfer with a four-membered ring transition state owning a free energy barrier of 32.73 kcal/mol, and the reaction pathway via a water bridge is not located. Meanwhile, the energy barriers increased for systems in which the N atom in heterocycle of primary amine is replaced by P/As atoms. The rate-determining step changes from the second hydrogen transfer step for N system to the first hydrogen transfer step for As system. The position effect of adjacent nitrogen atom is also investigated. The γ position owns the highest reactivity of the aldimine condensation, which implies that the ring strain plays an important role in the aldimine condensation of primary amine containing nitrogenous heterocycle with aldehyde. This theoretical study may provide insights to unveil the nature of aldimine condensation of aldehyde and primary amine owning nitrogeneous heterocycle.
- nitrogenous heterocycle,
- primary amine,
- aldimine condensation,
- DFT,
- hydrogen transfer
1. [1]
  Schiff, H. Justus Liebigs Ann. Chem. 1864, 131, 118. doi: 10.1002/jlac.18641310113
2. [2]
  Leth, L. A.; Naesborg, L.; Reyes-Rodriguez, G. J.; Tobiesen, H. N.; Iversen, M. V.; Jorgensen, K. A. J. Am. Chem. Soc. 2018, 140, 12687. doi: 10.1021/jacs.8b07394
3. [3]
  Rezayee, N. M.; Lauridsen, V. H.; Naesborg, L.; Nguyen, T. V. Q.; Tobiesen, H. N.; Jorgensen, K. A. Chem. Sci. 2019, 10, 3586. doi: 10.1039/C9SC00196D
4. [4]
  Liu, Y.; Yue, X.; Luo, C.; Zhang, L.; Lei, M. Energy Environ. Mater. 2019, 2, 292. doi: 10.1002/eem2.12050
5. [5]
  Stana, A.; Enache, A.; Vodnar, D. C.; Nastasa, C.; Benedec, D.; Ionut, I.; Login, C.; Marc, G.; Oniga, O.; Tiperciuc, B. Molecules 2016, 21, 1595. doi: 10.3390/molecules21111595
6. [6]
  Hong, M.; Min, J.; Wang, S. Chin. J. Org. Chem. 2018, 38, 1907(in Chinese).
7. [7]
  Li, Y.; Jia, F.; Ma, L.; Li, Z. Acta Chim. Sinica 2015, 73, 1311(in Chinese). doi: 10.3969/j.issn.0253-2409.2015.11.005
8. [8]
  Hu, S.-B.; Chen, M.-W.; Zhai, X.-Y.; Zhou, Y.-G. Acta Chim. Sinica 2018, 76, 103(in Chinese).
9. [9]
  Wang, H.; Huang, L. Chin. J. Org. Chem. 2019, 39, 883(in Chinese).
10. [10]
  Xiao, M.; Yue, X.; Xu, R.; Tang, W.; Xue, D.; Li, C.; Lei, M.; Xiao, J.; Wang, C. Angew. Chem., Int. Ed. 2019, 58, 10528. doi: 10.1002/anie.201905870
11. [11]
  Santerre, G. M.; Hansrote, C. J.; Crowell, T. I. J. Am. Chem. Soc. 1958, 80, 1254. doi: 10.1021/ja01538a056
12. [12]
  Martin, R. B. J. Phys. Chem. 1964, 68, 1369. doi: 10.1021/j100788a017
13. [13]
  Makela, M. J.; Korpela, T. K. Chem. Soc. Rev. 1983, 12, 309. doi: 10.1039/CS9831200309
14. [14]
  Jencks, W. P. Prog. Phys. Org. Chem. 1964, 2, 63.
15. [15]
  Hine, J.; Via, F. A.; Gotkis, J. K.; Craig, J. C. J. Am. Chem. Soc. 1970, 92, 5186. doi: 10.1021/ja00720a031
16. [16]
  Sayer, J. M.; Pinsky, B.; Schonbrunn, A.; Washtien, W. J. Am. Chem. Soc. 1974, 96, 7998. doi: 10.1021/ja00833a027
17. [17]
  Rosenberg, S.; Silver, S. M.; Sayer, J. M.; Jencks, W. P. J. Am. Chem. Soc. 1974, 96, 7986. doi: 10.1021/ja00833a026
18. [18]
  Williams, I. H. J. Am. Chem. Soc. 1987, 109, 6299. doi: 10.1021/ja00255a012
19. [19]
  Hall, N. E.; Smith, B. J. J. Phys. Chem. A 1998, 102, 4930. doi: 10.1021/jp9810825
20. [20]
  Jencks, W. P. J. Am. Chem. Soc. 1959, 81, 475. doi: 10.1021/ja01511a053
21. [21]
  Jencks, W. P. Acc. Chem. Res. 1976, 9, 425. doi: 10.1021/ar50108a001
22. [22]
  Sayer, J. M.; Jencks, W. P. J. Am. Chem. Soc. 1973, 95, 5637. doi: 10.1021/ja00798a031
23. [23]
  Ding, Y. Q.; Cui, Y. Z.; Li, T. D. J. Phys. Chem. A 2015, 119, 4252. doi: 10.1021/acs.jpca.5b02186
24. [24]
  Salva, A.; Donoso, J.; Frau, J.; Muñoz, F. J. Phys. Chem. A 2003, 107, 9409. doi: 10.1021/jp034769k
25. [25]
  Ortega-Castro, J.; Adrover, M.; Frau, J.; Salva, A.; Donoso, J.; Muñoz, F. J. Phys. Chem. A 2010, 114, 4634. doi: 10.1021/jp909156m
26. [26]
  Casasnovas, R.; Salvà, A.; Frau, J.; Donoso, J.; Muñoz, F. Chem. Phys. 2009, 355, 149. doi: 10.1016/j.chemphys.2008.12.006
27. [27]
  Solis-Calero, C.; Ortega-Castro, J.; Muñoz, F. J. Phys. Chem. B 2010, 114, 15879. doi: 10.1021/jp1088367
28. [28]
  Kirmizialtin, S.; Yildiz, B. S.; Yildiz, I. J. Phys. Org. Chem. 2017, 30, 1.
29. [29]
  Ciaccia, M.; Di Stefano, S. Org. Biomol. Chem. 2015, 13, 646. doi: 10.1039/C4OB02110J
30. [30]
  Hooley, R. J.; Iwasawa, T.; Rebek, J., Jr. J. Am. Chem. Soc. 2007, 129, 15330. doi: 10.1021/ja0759343
31. [31]
  Ciaccia, M.; Cacciapaglia, R.; Mencarelli, P.; Mandolini, L.; Di Stefano, S. Chem. Sci. 2013, 4, 2253. doi: 10.1039/c3sc50277e
32. [32]
  Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615. doi: 10.1039/b810189b
33. [33]
  Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378. doi: 10.1021/jp810292n
34. [34]
  Hratchian, H. P.; Schlegel, H. B. J. Chem. Phys. 2004, 120, 9918. doi: 10.1063/1.1724823
35. [35]
  Mayer, I. Chem. Phys. Lett. 1983, 97, 270. doi: 10.1016/0009-2614(83)80005-0
36. [36]
  Wiberg, K. B. Tetrahedron 1968, 24, 1083. doi: 10.1016/0040-4020(68)88057-3
37. [37]
  Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.22885
38. [38]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision B. 01. Gaussian, Inc., Wallingford, 2010.
39. [39]
  Legault, C. Y. CYLview, 1.0b, Université de Sherbrooke, 2009, http://www.cylview.org.
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