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Catalytic Glycosylation for Minimally Protected Donors and Acceptors

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Oligosaccharides have myriad functions throughout biology.1,2 To investigate these functions requires multi-step chemical synthesis of these structurally complex molecules. With a dense concentration of stereocentres and hydroxyl groups, oligosaccharide assembly through O-glycosylation requires simultaneous control of site-, stereo-, and chemoselectivities3,4. Chemists have traditionally relied on protecting group manipulations for this purpose,5–8 adding a lot of synthetic work. Here, we report a glycosylation platform that enables selective coupling between unprotected or minimally protected donor and acceptor sugars, producing 1,2-cis-O-glycosides in a catalyst-controlled, site-selective manner. Radical-based activation9 of allyl glycosyl sulfones forms glycosyl bromides. A designed aminoboronic acid catalysts bring this reactive intermediate close to an acceptor through a network of noncovalent hydrogen bonding and reversible covalent B–O bonding interactions, allowing precise glycosyl transfer. The site of glycosylation can be switched with different aminoboronic acid catalysts by affecting their interaction modes with substrates. The method accommodates a wide range of sugar types, amenable to preparing naturally occurring sugar chains and pentasaccharides containing 11 free hydroxyls. Experimental and computational studies provide insights into the origin of selectivity outcomes.

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Correspondence to Yun-Dong Wu or Dawen Niu.

Supplementary information

Supplementary Information

The file contains additional optimization results, detailed experimental procedures, compound characterization data, experimental and theoretical mechanistic results, as well as nuclear magnetic resonance spectra.

Supplementary Data 1

CIF file of compound 16A (CCDC no. 2303249).

Supplementary Data 2

CIF file of compound 16K (CCDC no. 2303245).

Supplementary Data 3

CIF file of compound 17c-OH (CCDC no. 2303235).

Supplementary Data 4

CIF file of compound SI-34 (CCDC no. 2322042).

Supplementary Data 5

CIF file of compound SI-49 (CCDC no. 2322044).

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Dang, QD., Deng, YH., Sun, TY. et al. Catalytic Glycosylation for Minimally Protected Donors and Acceptors. Nature (2024).

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