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.
|Titolo:||Psi[CH(CF3)NH]Gly-peptides : synthesis and conformation analysis|
BELLUCCI, MARIA CRISTINA (Secondo)
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Data di pubblicazione:||7-apr-2009|
|Digital Object Identifier (DOI):||10.1039/b901718f|
|Appare nelle tipologie:||01 - Articolo su periodico|