Synthesis of Docosasaccharide Arabinan Motif of Mycobacterial Cell Wall

• Published in: Journal of the American Chemical Society 2011-02, Vol.133 (7), p.2275-2291
• Main Authors: Ishiwata, Akihiro, Ito, Yukishige
• Format: Article
• Language: English
• Subjects: Amino Acid Motifs; Carbohydrate Sequence; Cell Wall - chemistry; Models, Molecular; Molecular Sequence Data; Mycobacterium - chemistry; Polysaccharides - chemical synthesis; Polysaccharides - chemistry; Stereoisomerism
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja109932t

Mycobacterial arabinan is a common constituent of both arabinogalactan (AG) and lipoarabinomannan (LAM). In this study, synthesis of β-Araf containing common arabinan docosasaccharide motif (22 Araf monomer units) of mycobacterial cell wall was achieved. Our synthetic strategy toward arabinan involves (1) the stereoselective β-arabinofuranosylation using both 3,5-O-TIPDS-protected and NAP-protected arabinofuranosyl donors for straightforward intermolecular glycosylation and intramolecular aglycon delivery (IAD), respectively, and (2) the convergent fragment coupling with branched fragments at the linear sequence using thioglycoside donor obtained from the corresponding acetonide at the reducing terminal of each fragment through a three-step procedure. Because the acetonide at the reducing terminal of all fragments would be converted to thioglycoside as the glycosyl donor, and mainly Bn ether protections were used, our strategy will be readily applicable to the synthesis of more complex arabinan, arabinogalactan, and arabinomycolate derived from mycobacterial CWS.