Conformational investigation of alpha,beta-dehydropeptides. VIII. N-acetyl-alpha,beta-dehydroamino acid N'-methylamides: conformation and electron density perturbation from infrared and theoretical studies.

The Fourier transform infrared spectra are analyzed in the regions of Vs(N-H), amide I, amide II and Vs(C alpha = C beta) bands for a series of Ac-delta Xaa-NHMe, where delta Xaa = delta Ala, (Z)-delta Abu, (Z)-delta Leu, (Z)-delta Phe and delta Val, to determine the predominant solution conformation of these alpha,beta-dehydropeptide-related molecules and the electron distribution perturbation in their amide bonds. The measurements were performed in dichloromethane (DCM). To confirm and rationalize the assignments, the spectra of the respective series of saturated Ac-Xaa-NHMe, recorded in DCM, and the spectra of these two series of unsaturated and saturated compounds, recorded in acetonitr…

Conformational investigation of α,β-dehydropeptides. IX. N-Acetyl-(E)-α,β-dehydrobutyrine N′-methylamide: stereoelectronic properties from infrared and theoretical studies*

The Fourier transform infrared spectra of Ac-(E)-deltaAbu-NHMe were analyzed to determine the predominant solution conformation(s) of this (E)-alpha,beta-dehydropeptide-related compound and the electron density perturbation in its amide groups. The measurements were performed in dichloromethane and acetonitrile in the region of mode vs (N-H), amide I, amide II and vs (C(alpha)=Cbeta). The equilibrium geometrical parameters, calculated by a method based on the density functional theory with the B3LYP functional and the 6-31G* basis set, were used to support spectroscopic interpretation and gain some deeper insight into the molecule. The experimental and theoretical data were compared with th…

Synthesis of peptides with α,β-dehydroamino acids, VI. Synthesis ofN-benzyloxycarbonyl andN-trifluoroacetyl dipeptides of α,β-dehydro-butyrine, -valine, -leucine, and -isoleucine

Condensation of Z- and TFA-amino acid amides with 2-oxo-acids, namely butanoic, 3-methylbutanoic, 4-methylpentanoic, and (3RS)-3-methylpentanoic acid, yields (in the presence of p-toluenesulfonic acid as a catalyst) Z- and TFA-dipeptides with C-terminal ΔAbu2) (1–4), ΔVal (5–8), ΔLeu (9–11), and ΔIle (12–15) (Table 1).

LOWER ALIPHATIC 2-OXOACIDS AND THEIR ETEYL ESTERS FROM ETHYL ESTERS OF 2-HYDROXY ACIDS

(1989). LOWER ALIPHATIC 2-OXOACIDS AND THEIR ETEYL ESTERS FROM ETHYL ESTERS OF 2-HYDROXY ACIDS. Organic Preparations and Procedures International: Vol. 21, No. 1, pp. 75-82.

Co-ordination of copper(II) ions by prolyl-α,β-dehydroamino acids: comparative studies and general considerations

Potentiometric and spectroscopic measurements and theoretical calculations have revealed that α,β-dehydroamino acid residues have a considerable effect on the co-ordination ability of an adjacent amide nitrogen towards Cu2+ ions. Also the side chain of such residues affects the stability constants and, in some cases, the binding mode of short peptides containing α,β-dehydroamino acid residues. The theoretical calculations showed that all dehydroamino acids except α,β-dehydroalanine tend to bend a peptide chain towards a turn conformation. This has a very strong impact on the co-ordination ability of a dehydropeptide ligand.

Unusual binding ability of α,β-dehydrodipeptides towards metal ions

Abstract Ni II , Zn II and Co II complexes of α,β-dehydro-dipeptides (containing Gly, Leu, Ala, Val or Phe residues) were studied by potentiometric and spectroscopic methods. Deprotonation and coordination of amide nitrogens occurred in all cases around the physiological pH range. The dipeptides with composition of Xaa-Δ-Ala formed octahedral species, while Gly-Δ-Xaa (Xaa = Leu or Phe) formed square planar bis complexes with Ni II .

N-Acetyl-α, β-dehydroamino acid N’-methylamides and N’, N’-Dimethylamides