Chiral-auxiliary-mediated 1,2-cis-glycosylations for the solid-supported synthesis of a biologically
Author: ["Thomas J. Boltje","Jin-Hwan Kim","Jin Park","Geert-Jan Boons"]
Publication: Nature Chemistry
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Abstract
Solid-phase oligosaccharide synthesis offers the promise of providing libraries of oligosaccharides for glycomics research. A major stumbling block to solid-phase oligosaccharide synthesis has been a lack of general methods for the stereoselective installation of 1,2-cis-glycosides, and intractable mixtures of compounds are obtained if several such glycosides need to be installed. We have prepared on-resin a biologically important glucoside containing multiple 1,2-cis-glycosidic linkages with complete anomeric control by using glycosyl donors having a participating (S)-(phenylthiomethyl)benzyl chiral auxiliary at C2. A branching point could be installed by using 9-fluorenylmethyloxycarbonyl (Fmoc) and allyloxycarbonyl (Alloc) as a versatile set of orthogonal protecting groups. The synthetic strategy made it possible to achieve partial on-resin deprotection of the completed oligosaccharide, thereby increasing the overall efficiency of the synthesis. The combination of classical and auxiliary-mediated neighbouring-group participation for controlling anomeric selectivity is bringing the promise of routine automated solid-supported oligosaccharide synthesis closer. The difficulty in the stereoselective introduction of 1,2-cis-glycosides is a major stumbling block in the solid-supported synthesis of oligosaccharides. Now, this has been achieved for a biologically important glucoside containing multiple 1,2-cis-glycosidic linkages with complete anomeric control by using glycosyl donors having a participating (S)-(phenylthiomethyl)benzyl chiral auxiliary at C-2.
Cite this article
Boltje, T., Kim, JH., Park, J. et al. Chiral-auxiliary-mediated 1,2-cis-glycosylations for the solid-supported synthesis of a biologically important branched α-glucan. Nature Chem 2, 552–557 (2010). https://doi.org/10.1038/nchem.663
