Chemistry of 1,2- and 4,5-unsaturated sugars: Access to labeled and rare pyranosides
Abstract
1,2-unsaturated hexopyranoses derived from D-glucose (glycals) were utilized for the synthesis of [13C]methyl 2-[15 N]amino-2-deoxy-β-D-glucopyranoside derivatives using 13CH3I and (saltmen)Mn(15N) as isotope sources. The glycosidic conformations of [13C]methyl 2-[15N]acetamido-2-deoxy-β-D-glucopyranoside have been evaluated in a frozen aqueous matrix using REDOR spectroscopy. 4,5-unsaturated pentopyranoses (4-deoxypentenosides) have also been utilized in the synthesis of isotopically labeled and rare sugars based on a two-step epoxidation-nucleophilic ring opening sequence, leading to L-sugars with a wide range of functional groups at C5. This chemistry has led to the synthesis of L-glycals from D-glycals via a one-carbon degradation (decarboxylative elimination) of a pseudo symmetric β-C-glycoside intermediate. The synthetic utility of L-glycals and 4-deoxypentenosides has been demonstrated in the synthesis of the H-type II mirror-image trisaccharide.
Degree
Ph.D.
Advisors
Wei, Purdue University.
Subject Area
Organic chemistry
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