title: Glaser oxidative coupling on peptides: stabilization of β-turn structure via a 1,3-butadiyne constraint.
abstract: The Glaser-Eglinton reaction between either two C or N propargylglycine (Pra or NPra) amino acids, in the presence of copper(II), led to cyclic hexa- and octapeptides constrained by a butadiyne bridge. The on-resin cyclization conditions were analyzed and optimized. The consequences of this type of constraint on the three dimensional structure of these hexapeptides and octapeptides were analyzed in details by NMR and molecular dynamics. We show that stabilized short cyclic peptides could be readily prepared via the Glaser oxidative coupling either with a chiral (Pra), or achiral (NPra) residue. The 1,3-butadiyne cyclization, along with disulfide bridged and lactam cyclized hexapeptides expands the range of constrained peptides that will allow exploring the breathing of amino acids around a β-turn structure.
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, 24, rue Lhomond, 75005 Paris, France; Sorbonne Universités, UPMC Univ Paris 06, LBM, 4 place Jussieu, F-75005 Paris, France; CNRS, UMR 7203 LBM, F-75005 Paris, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Auberger
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, 24, rue Lhomond, 75005 Paris, France; Sorbonne Universités, UPMC Univ Paris 06, LBM, 4 place Jussieu, F-75005 Paris, France; CNRS, UMR 7203 LBM, F-75005 Paris, France; PeptLab-SOSCO EA4505 University of Florence Via della Lastruccia 13, I-50019 Sesto F.no, Italy and University of Cergy-Pontoise, 5 Mail Gay Lussac, F-95031 Cergy-Pontoise CEDEX, France.
authors.forename: Margherita
authors.initials: M
authors.lastname: Di Pisa
authors.affiliation: PeptLab-SOSCO EA4505 University of Florence Via della Lastruccia 13, I-50019 Sesto F.no, Italy and University of Cergy-Pontoise, 5 Mail Gay Lussac, F-95031 Cergy-Pontoise CEDEX, France.
authors.forename: Maud
authors.initials: M
authors.lastname: Larregola
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, 24, rue Lhomond, 75005 Paris, France; Sorbonne Universités, UPMC Univ Paris 06, LBM, 4 place Jussieu, F-75005 Paris, France; CNRS, UMR 7203 LBM, F-75005 Paris, France.
authors.forename: Gérard
authors.initials: G
authors.lastname: Chassaing
authors.affiliation: PeptLab-SOSCO EA4505 University of Florence Via della Lastruccia 13, I-50019 Sesto F.no, Italy and University of Cergy-Pontoise, 5 Mail Gay Lussac, F-95031 Cergy-Pontoise CEDEX, France.
authors.forename: Elisa
authors.initials: E
authors.lastname: Peroni
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, 24, rue Lhomond, 75005 Paris, France; Sorbonne Universités, UPMC Univ Paris 06, LBM, 4 place Jussieu, F-75005 Paris, France; CNRS, UMR 7203 LBM, F-75005 Paris, France.
authors.forename: Solange
authors.initials: S
authors.lastname: Lavielle
authors.affiliation: PeptLab-SOSCO EA4505 University of Florence Via della Lastruccia 13, I-50019 Sesto F.no, Italy and University of Cergy-Pontoise, 5 Mail Gay Lussac, F-95031 Cergy-Pontoise CEDEX, France.
authors.forename: Anna-Maria
authors.initials: AM
authors.lastname: Papini
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, 24, rue Lhomond, 75005 Paris, France; Sorbonne Universités, UPMC Univ Paris 06, LBM, 4 place Jussieu, F-75005 Paris, France; CNRS, UMR 7203 LBM, F-75005 Paris, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Lequin
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, 24, rue Lhomond, 75005 Paris, France; Sorbonne Universités, UPMC Univ Paris 06, LBM, 4 place Jussieu, F-75005 Paris, France; CNRS, UMR 7203 LBM, F-75005 Paris, France.
authors.forename: Jean-Maurice
authors.initials: JM
authors.lastname: Mallet
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D000595:Amino Acid Sequence; D003300:Copper / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D056004:Molecular Dynamics Simulation; D058451:Oxidative Coupling; D010456:Peptides, Cyclic / Q000138:chemical synthesis / Q000737:chemistry*; D017433:Protein Structure, Secondary
chemical_list: D000480:Alkynes; D010456:Peptides, Cyclic; D003300:Copper
keywords: Constraint; Glaser oxidative coupling; NMR studies; Peptides; β-Turn structure