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Title: Zinc(II) iodide-firected β-mannosylation: reaction selectivity, mode, and application
Authors: Zhong, Xuemei
Zhou, Siai
Ao, Jiaming
Guo, Aoxin
Xiao, Qian
Huang, Yan
Zhu, Wanmeng
Cai, Hui
Ishiwata, Akihiro
Ito, Yukishige
Liu, Xue-Wei
Ding, Feiqing
Keywords: Science::Chemistry
Issue Date: 2021
Source: Zhong, X., Zhou, S., Ao, J., Guo, A., Xiao, Q., Huang, Y., Zhu, W., Cai, H., Ishiwata, A., Ito, Y., Liu, X. & Ding, F. (2021). Zinc(II) iodide-firected β-mannosylation: reaction selectivity, mode, and application. Journal of Organic Chemistry, 86(23), 16901-16915.
Journal: Journal of Organic Chemistry 
Abstract: A direct, efficient, and versatile glycosylation methodology promises the systematic synthesis of oligosaccharides and glycoconjugates in a streamlined fashion like the synthesis of medium to long-chain nucleotides and peptides. The development of a generally applicable approach for the construction of 1,2-cis-glycosidic bond with controlled stereoselectivity remains a major challenge, especially for the synthesis of β-mannosides. Here, we report a direct mannosylation strategy mediated by ZnI2, a mild Lewis acid, for the highly stereoselective construction of 1,2-cis-β linkages employing easily accessible 4,6-O-tethered mannosyl trichloroacetimidate donors. The versatility and effectiveness of this strategy were demonstrated with successful β-mannosylation of a wide variety of alcohol acceptors, including complex natural products, amino acids, and glycosides. Through iteratively performing ZnI2-mediated mannosylation with the chitobiosyl azide acceptor followed by site-selective deprotection of the mannosylation product, the novel methodology enables the modular synthesis of the key intermediate trisaccharide with Man-β-(1 → 4)-GlcNAc-β-(1 → 4)-GlcNAc linkage for N-glycan synthesis. Theoretical investigations with density functional theory calculations delved into the mechanistic details of this β-selective mannosylation and elucidated two zinc cations' essential roles as the activating agent of the donor and the principal mediator of the cis-directing intermolecular interaction.
ISSN: 0022-3263
DOI: 10.1021/acs.joc.1c02091
Schools: School of Physical and Mathematical Sciences 
Rights: © 2021 American Chemical Society. All rights reserved.
Fulltext Permission: none
Fulltext Availability: No Fulltext
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