Enhanced intramolecular amide-amide hydrogen bonding through cooperativity

Tetrahedron Letters

Volumn 37, Issue 13, 1996, Pages 2189-2192

  Gung, Benjamin W ^a   Zhu, Zhaohai ^a  

^a MIAMI UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; INFRARED SPECTROPHOTOMETRY; NUCLEAR MAGNETIC RESONANCE; PEPTIDE SYNTHESIS; PROTEIN STRUCTURE;

EID: 0029923905     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00256-0     Document Type: Article

References (15)

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9. (b) Schafer, L.; Newton, S. Q.; Cao, M.; Peeters, A.; Alsenoy, C. V.; Wolinski, K.; Momany, F. A. J. Am. Chem. Soc. 1993, 115, 272-280.
10. For related experimental studies, see: (a) Mathias, J. P.; Seto, C. T.; Simanek, E. E.; Whitesides, G. M. J. Am. Chem. Soc. 1994, 116, 1725-36.
11. (b) Domingo, J. C.; Mora, M.; Africa de Madariaga, M. Chem. Phys. Lipids 1994, 69, 229-40.
12. 11
13. Ugi, I.; Domling, A.; Horl, W. Endeaver, New Series, 1994, 18, 115.
14. Gellman, S. H.; Dado, G. P.; Liang, G.; Adams, B. R. J. Am. Chem. Soc. 1991, 113, 1164.
15. A reviewer has suggested that the enhanced intramolecular amide-amide hydrogen bonding of the diamides 3 and 4 are due to the conformational restriction from the five-membered ring between the α-hydroxy and the amide carbonyl group. Our ab initio (MP2/6-31*) calculations show a difference of only 0.7 kcal/mol for the two conformers of glycolic amide. This means that both forms are equation presented available to diamide 3 and 4. Therefore, we believe that it is hydrogen bonding cooperativity which enhances the intramolecular amide-amide H-bond. Furthermore, it is not clear how can one clearly separate hydrogen bonding cooperativity from conformational restriction. For example, in the initiation process of an α-helical peptide, the establishment of the first hydrogen bond certainly restricts the conformation to the advantage of the second H-bond formation. However, this process is normally considered as hydrogen bonding cooperativity, rather than conformational restriction.