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Synthesis 2010(18): 3143-3151  
DOI: 10.1055/s-0030-1258174
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Bernhard Müllera, Markus Blaukopfa, Andreas Hofingera, Alla Zamyatinaa, Helmut Bradeb, 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;
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Publication History

Received 21 April 2010
Publication Date:
16 July 2010 (online)

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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, SN2 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