- Article
- Published:
- Qiu-Di Dang1na1,
- Yi-Hui Deng2,3na1,
- Tian-Yu Sun2,3,
- Yao Zhang1,
- Jun Li1,
- Xia Zhang ORCID: orcid.org/0000-0002-5073-02691,
- Yun-Dong Wu ORCID: orcid.org/0000-0003-4477-73322,3 &
- …
- Dawen Niu ORCID: orcid.org/0000-0002-5114-44131
Nature (2024)Cite this article
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Subjects
- Carbohydrate chemistry
- Organocatalysis
- Chemical synthesis
Abstract
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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Author information
Author notes
These authors contributed equally: Qiu-Di Dang, Yi-Hui Deng
Authors and Affiliations
State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, and School of Chemical Engineering, Sichuan University, Chengdu, China
Qiu-Di Dang,Yao Zhang,Jun Li,Xia Zhang&Dawen Niu
The Key Laboratory of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomic, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, China
Yi-Hui Deng,Tian-Yu Sun&Yun-Dong Wu
Institute of Molecular Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, China
Yi-Hui Deng,Tian-Yu Sun&Yun-Dong Wu
Authors
- Qiu-Di Dang
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- Yi-Hui Deng
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- Tian-Yu Sun
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- Yao Zhang
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- Jun Li
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- Xia Zhang
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- Yun-Dong Wu
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- Dawen Niu
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Corresponding authors
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). https://doi.org/10.1038/s41586-024-07695-4
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DOI: https://doi.org/10.1038/s41586-024-07695-4
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