Ring-Opening of Aziridine -2 -Carboxamides by Carbohydrate C1-O Nucleophiles. Stereoselective Preparation of O-Linked Glycopeptides
type: CreativeWork
description: A new method for the synthesis of O-linked glycopeptides is described. The method uses the carbohydrate C1-O nucleophilic ring-opening of aziridine-2-carboxamides to access the target O-linked glycopeptides. The synthesis of the alpha-GalNAc-Ser class of glycopeptides is emphasized and either the alpha- or beta-glycoside can be accessed by judicious selection of solvent and metal counter-ion, even in the presence of the native carbohydrate C2-NHAc group. Other classes of 0-glycosyl serine constructs, such as the beta-GlcNAc-Ser and alpha-Man-Ser linkages, are also prepared by this approach. In the course of these studies, the ortho-allylbenzyl (ABn) moiety was developed as a new C-terminus secondary amide protective group for carboxylic acids, which allows for oxidative C-terminus extension of amino acids following the carbohydrate-aziridine coupling reaction. A new protocol for deprotection of p-nitrobenzenesulfonamides with in situ peptide coupling is also reported. This reaction allows for direct N-terminus extension of p-nitrobenzenesulfonyl protected amino acids, or glycosyl amino acids, in one synthetic step.
abstract: A new method for the synthesis of O-linked glycopeptides is described. The method uses the carbohydrate C1-O nucleophilic ring-opening of aziridine-2-carboxamides to access the target O-linked glycopeptides. The synthesis of the alpha-GalNAc-Ser class of glycopeptides is emphasized and either the alpha- or beta-glycoside can be accessed by judicious selection of solvent and metal counter-ion, even in the presence of the native carbohydrate C2-NHAc group. Other classes of 0-glycosyl serine constructs, such as the beta-GlcNAc-Ser and alpha-Man-Ser linkages, are also prepared by this approach. In the course of these studies, the ortho-allylbenzyl (ABn) moiety was developed as a new C-terminus secondary amide protective group for carboxylic acids, which allows for oxidative C-terminus extension of amino acids following the carbohydrate-aziridine coupling reaction. A new protocol for deprotection of p-nitrobenzenesulfonamides with in situ peptide coupling is also reported. This reaction allows for direct N-terminus extension of p-nitrobenzenesulfonyl protected amino acids, or glycosyl amino acids, in one synthetic step.
author: Ryan, Daniel
language: eng
keywords: Chemistry, Organic
date published: 2015-09-25T22:14:00Z
date modified: 2026-07-22T22:26:23Z
provider: University of Illinois - Urbana-Champaign
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Illinois at Urbana-Champaign

PropertyValue
property ID: Handle
value: http://hdl.handle.net/2142/84338