Highly Stereoselective 1,2‐cis‐Xylosylation Enabled by Reagent Modulation, Remote Participation, and Electron‐Withdrawing Synergistic Effects

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AbstractStereoselective 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 SN1 and SN2 pathways.