Gas-Phase Intercluster Thiyl-Radical Induced C–H Bond Homolysis Selectively Forms Sugar C2-Radical Cations of Methyl D-Glucopyranoside: Isotopic Labeling Studies and Cleavage Reactions

Abstract

A suite of isotopologues of methyl D-glucopyranosides is used in conjunction with multistage mass spectrometry experiments to determine the radical site and cleavage reactions of sugar radical cations formed via a recently developed ‘bio-inspired’ method. In the first stage of CID (MS 2 ), collision-induced dissociation (CID) of a protonated noncovalent complex between the sugar and S-nitrosocysteamine, [H 3 NCH 2 CH 2 SNO + M] + , unleashes a thiyl radical via bond homolysis to give the noncovalent radical cation, [H 3 NCH 2 CH 2 S • + M] + . CID (MS 3 ) of this radical cation complex results in dissociation of the noncovalent complex to generate the sugar radical cation. Replacement of all..