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Volumn , Issue 6, 2000, Pages 1021-1031

Synthesis and binding properties of a macrobicyclic receptor for N-protected peptides with a carboxylic acid terminus

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACIDS; DERIVATIVES; HYDROGEN BONDS; NUCLEAR MAGNETIC RESONANCE; SYNTHESIS (CHEMICAL); TITRATION;

EID: 0034696502     PISSN: 14704358     EISSN: None     Source Type: Journal    
DOI: 10.1039/a908090b     Document Type: Article
Times cited : (20)

References (45)
  • 18
    • 0001201464 scopus 로고
    • Although the dicyclohexylcarbodiimide coupling proved the method of choice in this instance, we have had difficulties coupling other amino acids with diaminopyridine and have found that the most reliable method involves preactivation of the diaminopyridine with bis(trimethylsilyl)acetamide (S. Rajeswari, R. J. Jones and M. P. Cava, Tetrahedron Lett., 1987, 28, 5099) and coupling with the acid fluoride derived from the amino acid by treatment with cyanuric fluoride
    • (1987) Tetrahedron Lett. , vol.28 , pp. 5099
    • Rajeswari, S.1    Jones, R.J.2    Cava, M.P.3
  • 28
    • 33645950870 scopus 로고
    • University of Pittsburgh, USA, © C. S. Wilcox and the University of Pittsburgh
    • Hostest 5 software: C. S. Wilcox and N. M. Glagovich, University of Pittsburgh, USA, © C. S. Wilcox and the University of Pittsburgh, 1993. See also
    • (1993)
    • Wilcox, C.S.1    Glagovich, N.M.2
  • 31
    • 33645898730 scopus 로고    scopus 로고
    • note
    • 2 symmetry, so that while a hydrogen bond is only formed with one of two symmetrically related protons, the NMR reports the time-averaged signal for the hydrogen-bonded and non-hydrogen bonded partner.
  • 32
    • 33645956635 scopus 로고    scopus 로고
    • note
    • In the case of the titration experiment with what turned out to be the most tightly bound substrate, Cbz-β-alanyl-D-alanine, we did monitor the shift of the phenylalanyl α-proton (Δδ = 0.4) and the aromatic rim proton ortho to the carboxamide (Δδ= -0.12). Analysis of the resulting data gave association constants in agreement with those determined from monitoring the amidopyridine NH, but the quality of the fit for the data from the phenylalanyl α-proton and aromatic rim proton was not as good, due to loss of resolution and the presence of overlapping signals from both host and guest protons as the titration progressed.
  • 33
    • 12044255753 scopus 로고
    • Comparison of binding constants of structurally different carboxylic acids should be treated with some caution since the strength of the interaction with the amidopyridine unit will be influenced by the acidity of the carboxylic acid moiety (see e.g., M. H. Abraham, Chem. Soc. Rcr., 1993, 22, 73;
    • (1993) Chem. Soc. Rcr. , vol.22 , pp. 73
    • Abraham, M.H.1
  • 35
    • 33645941009 scopus 로고    scopus 로고
    • note
    • Thus, for example, the difference in binding strength of hexanoic and phenylacetic acid may be partly due to the difference in their acidities. However, the differences in acidities, in chloroform solution, of closely related amino acid substrates are likely to be small and are unlikely to lead to differences in the interaction with the amidopyridine unit which exceed the error in the experimentally determined binding constants and clearly for enantiomers of the same substrate the acidities will be the same.


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