Catalytic glycosylation for minimally protected donors and acceptors

Qiu-Di Dang, Yi-Hui Deng, Tian-Yu Sun, Yao Zhang, Jun Li, Xia Zhang, Yun-Dong Wu () and Dawen Niu ()
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Qiu-Di Dang: Sichuan University
Yi-Hui Deng: Peking University Shenzhen Graduate School
Tian-Yu Sun: Peking University Shenzhen Graduate School
Yao Zhang: Sichuan University
Jun Li: Sichuan University
Xia Zhang: Sichuan University
Yun-Dong Wu: Peking University Shenzhen Graduate School
Dawen Niu: Sichuan University

Nature, 2024, vol. 632, issue 8024, 313-319

Abstract: Abstract Oligosaccharides have myriad functions throughout biological processes1,2. Chemical synthesis of these structurally complex molecules facilitates investigation of their functions. 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 purpose5–8, adding considerable 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 catalyst brings this reactive intermediate close to an acceptor through a network of non-covalent 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 the preparation of naturally occurring sugar chains and pentasaccharides containing 11 free hydroxyls. Experimental and computational studies provide insights into the origin of selectivity outcomes.

Date: 2024
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DOI: 10.1038/s41586-024-07695-4

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