Concise and Efficient Synthesis of 2-Acetamido-2-deoxy-β-d-hexopyranosides of Diverse Aminosugars from 2-Acetamido-2-deoxy-β-d-glucose

Abstract

The furanose acetonide derivative 1 is readily prepared from 2-acetamido-2-deoxy-D-glucose on a large scale without the need for chromatography. Mesylation of 1 provides an efficient, concise, synthetic route to rare 2-acetamido-2-deoxy-beta-D-hexopyranosides (2 and 3) via the corresponding methyl 2-acetamido-2-deoxy-3-O-methanesulfonyl-beta-D-glucopyranoside and subsequent inversion of configuration by direct displacement or formation of a 3,4-epoxide. Opening of this epoxide by azide provided a direct route to methyl 2-acetamido-4-amino-2,4,6-trideoxy-beta-D-gulopyranoside 4. Benzylation of 1 followed by ring expansion to the glucopyranoside, deoxygenation at C-6, and subsequent displacement of a C-4 triflate permitted the synthesis of methyl 2-acetamido-4-amino-2,4,6-trideoxy-beta-D-galactopyranoside 5. Methyl 2-acetamido-2-deoxy-beta-D-glucopyranoside available from 1 in quantitative yield was readily converted to methyl 2-acetamido-2-deoxy-beta-D-galactopyranoside 6 (>60%) by inversion of configuration at C-4. Introduction of a lactyl substituent at C-3 of oxazoline 1 also provides a facile synthesis of the biologically important muramic acid beta-glycoside 7. An interesting reaction to convert 2-acetamido-2-deoxyhexopyranosides to the corresponding 2-deoxy-2-tetrazole is also reported.