Efficient Synthesis of 4-Amino-4-deoxy-l-arabinose and Spacer-Equipped 4-Amino-4-deoxy-l-arabinopyranosides by Transglycosylation
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Bernhard Müller; Markus Blaukopf; Andreas Hofinger; Alla Zamyatina; Helmut Brade; Paul Kosma

doi:10.1055/s-0030-1258174

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Efficient Synthesis of 4-Amino-4-deoxy-l-arabinose and Spacer-Equipped 4-Amino-4-deoxy-l-arabinopyranosides by Transglycosylation Reactions

Bernhard Müller^a, Markus Blaukopf^a, Andreas Hofinger^a, Alla Zamyatina^a, Helmut Brade^b, Paul Kosma*^a
^a Department of Chemistry, University of Natural Resources and Applied Life Sciences-Vienna, Muthgasse 18, 1190 Vienna, Austria
^b Research Center Borstel, Leibniz Center for Medicine and Biosciences, Parkallee 22, 23845 Borstel, Germany
Fax: +43(1)476546059; e-Mail: paul.kosma@boku.ac.at;

Abstract

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Abstract

Methyl 4-azido-4-deoxy-β-l-arabinopyranoside has been synthesized in five steps starting from methyl β-d-xylopyranoside in a multigram scale without chromatographic purification in 78% overall yield. The transformation relied on selective tosylation/nosylation at O-4 followed by acylation, S_N2 displacement with sodium azide, and subsequent deprotection. The methyl 4-azido-4-deoxy-arabinoside was then converted into allyl, propenyl, ω-bromohexyl, and chloroethoxyethyl spacer glycosides by transglycosylation with the respective alcohols in good yields and fair anomeric selectivity. Reduction of the azido group and further transformations of the aglycone afforded ω-thiol-containing spacer derivatives. Coupling to maleimide-activated BSA provided a potent immunogen, which was used to generate murine and rabbit polyclonal sera binding to LPS-core epitopes containing 4-amino-4-deoxy-arabinose residues.

Key words

aminoarabinose - neoglycoconjugate - transglycosylation - lipopolysaccharide - spacer

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