Stereoselective synthesis of 2,3-diamino-2,3-dideoxy-β-D-mannopyranosyl uronates
Marthe T C Walvoort1, Gert-Jan Moggré, Gerrit Lodder
1Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Abstract:
With the aim to find an efficient synthetic procedure for the construction of 2,3-diamino-2,3-dideoxy-β-D-mannuronic acids, we evaluated three mannosyl donors: (S)-phenyl 4,6-di-O-acetyl-2,3-diazido mannopyranoside, (S)-phenyl 2,3-diazido-4,6-O-benzylidene mannopyranoside, and (S)-phenyl 2,3-diazido mannopyranosyl methyl uronate. The first two mannosylating agents are rather unselective or slightly α-selective in their condensation with three different acceptors. The mannuronic acid donor on the other hand reliably provides the desired β-mannosidic linkage. A mechanistic rationale is put forward to account for the different behavior of the three donor types. Suitably protected 2,3-diazido mannuronic acids were employed to construct the all-cis-linked tetrasaccharide repeating unit of the capsular polysaccharide of Bacillus stearothermophilus , featuring two 2,3-diacetamido-2,3-dideoxy-β-D-mannuronic acids.
Related Concept Videos
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
Biosynthesis of Polysaccharides
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Oligosaccharide Assembly
Multiple sugar molecules that may or may...


