Stereoselective constructions of 1,2-cis-glycosidic bonds are long-standing challenges in chemical synthesis. In particular, achieving highly stereoselective 1,2-cis-xylosylation remains a difficult task in carbohydrates chemistry. Here, we report that highly stereoselective 1,2-cis-xylosylation could be achieved via synergistic combinations of reagent modulation, remote participation, and electron-withdrawing effects. A variety of α-xylosides motifs have been effectively prepared by this 1,2-cis-xylosylation protocol, including hemicellulose xyloglucan, xyloglucosyl trisaccharide motif from mammalian cells, core M3 matriglycan motif, and even α-(1→3)-xylosides up to 12-mer. Furthermore, DFT calculations provided the origins of this stereoselective and synergistic 1,2-cis-xylosylation through S1 and S2 pathways.
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