Glaser oxidative coupling on peptides: Stabilization of β-turn structure via a 1,3-butadiyne constraint

被引：12

作者：

Auberger, Nicolas ^{[1
,2
,3
]}

Di Pisa, Margherita ^{[1
,2
,3
,4
,5
]}

Larregola, Maud ^{[4
,5
]}

Chassaing, Gerard ^{[1
,2
,3
]}

Peroni, Elisa ^{[4
,5
]}

Lavielle, Solange ^{[1
,2
,3
]}

Papini, Anna-Maria ^{[4
,5
]}

Lequin, Olivier ^{[1
,2
,3
]}

Mallet, Jean-Maurice ^{[1
,2
,3
]}

机构：

[1] PSL Res Univ, Ecole Normale Super, Dept Chim, F-75005 Paris, France

[2] Univ Paris 06, Sorbonne Univ, LBM, F-75005 Paris, France

[3] CNRS, UMR LBM 7203, F-75005 Paris, France

[4] Univ Florence, PeptLab SOSCO EA4505, I-50019 Sesto Fiorentino, Italy

[5] Univ Cergy Pontoise, F-95031 Cergy Pontoise, France

来源：

BIOORGANIC & MEDICINAL CHEMISTRY | 2014年 / 22卷 / 24期

关键词：

beta-Turn structure; Peptides; Constraint; Glaser oxidative coupling; NMR studies; RING-CLOSING METATHESIS; TERMINAL ALKYNES; 1,4-DISUBSTITUTED 1,3-DIYNES; ORGANIC-SYNTHESIS; DISULFIDE BONDS; AMINO-ACIDS; CYCLOADDITION; STABILITY; MIMICS; ACETYLENES;

D O I：

10.1016/j.bmc.2014.10.026

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

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 beta-turn structure. (C) 2014 Elsevier Ltd. All rights reserved.

引用

页码：6924 / 6932

页数：9

共 45 条

[1] Influence of Bases and Ligands on the Outcome of the Cu(I)-Catalyzed Oxidative Homocoupling of Terminal Alkynes to 1,4-Disubstituted 1,3-Diynes Using Oxygen as an Oxidant [J].