Psi[CH(CF3)NH]Gly peptides, a conceptually new class of peptidomimetics having a stereogenictrifluoroethylamine group as a natural peptide-bond surrogate, have been synthesized by stereoselective addition of a-amino acid esters to trans-3,3,3-trifluoro-1-nitropropene. Long range nuclear Overhauser effects, detected via ROESY experiments, provided evidence that model W[CH(CF3)NH]Glytetrapeptides incorporating a trifluoroethylamine mimic of the dipeptide loop Pro-Gly can be represented by an ensemble of unfolded and folded conformations. The latter are driven by the formation of a hydrogen bond between a carbonyl group and the aminic proton of the trifluoroethylamine unit. MD calculations indicate a population of conformers which adopt folded b turn structures for all the L-peptides; on the other hand, a D-stereochemistry at the Pro residue induces a natural folding towards a b hairpin conformation driven by the formation of a second hydrogen bond, regardless of the stereochemistry of the stereogenic peptide bond surrogate.
Psi[CH(CF3)NH]Gly-peptides : synthesis and conformation analysis / M. Molteni, M. C. Bellucci, S. Bigotti, S. Mazzini, A. Volonterio, M. Zanda. - In: ORGANIC & BIOMOLECULAR CHEMISTRY. - ISSN 1477-0520. - 7:11(2009 Apr 07), pp. 2286-2296.
Psi[CH(CF3)NH]Gly-peptides : synthesis and conformation analysis
M. C. BellucciSecondo
;S. Mazzini;
2009
Abstract
Psi[CH(CF3)NH]Gly peptides, a conceptually new class of peptidomimetics having a stereogenictrifluoroethylamine group as a natural peptide-bond surrogate, have been synthesized by stereoselective addition of a-amino acid esters to trans-3,3,3-trifluoro-1-nitropropene. Long range nuclear Overhauser effects, detected via ROESY experiments, provided evidence that model W[CH(CF3)NH]Glytetrapeptides incorporating a trifluoroethylamine mimic of the dipeptide loop Pro-Gly can be represented by an ensemble of unfolded and folded conformations. The latter are driven by the formation of a hydrogen bond between a carbonyl group and the aminic proton of the trifluoroethylamine unit. MD calculations indicate a population of conformers which adopt folded b turn structures for all the L-peptides; on the other hand, a D-stereochemistry at the Pro residue induces a natural folding towards a b hairpin conformation driven by the formation of a second hydrogen bond, regardless of the stereochemistry of the stereogenic peptide bond surrogate.Pubblicazioni consigliate
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