Recent advances in stereoselective 1,2- cis - O -glycosylations

• Published in: Frontiers in chemistry 2022-08, Vol.10, p.972429
• Main Authors: Ishiwata, Akihiro, Tanaka, Katsunori, Ao, Jiaming, Ding, Feiqing, Ito, Yukishige
• Format: Article
• Language: English
• Subjects: 1,2-cis glycosylation; bimodal glycosylation; Chemistry; intramolecular aglycon delivery (IAD); method for activation of glycosylation; stereoselective assembly
• ISSN: 2296-2646; 2296-2646
• DOI: 10.3389/fchem.2022.972429

For the stereoselective assembly of bioactive glycans with various functions, 1,2- - -glycosylation is one of the most essential issues in synthetic carbohydrate chemistry. The -configured -glycosidic linkages to the substituents at two positions of the non-reducing side residue of the glycosides such as α-glucopyranoside, α-galactopyranoside, β-mannopyranoside, β-arabinofuranoside, and other rather rare glycosides are found in natural glycans, including glycoconjugate (glycoproteins, glycolipids, proteoglycans, and microbial polysaccharides) and glycoside natural products. The way to 1,2- isomers is well sophisticated by using the effect of neighboring group participation from the most effective and kinetically favored C-2 substituent such as an acyl group, although high stereoselective synthesis of 1,2- glycosides without formation of 1,2- isomers is far less straightforward. Although the key factors that control the stereoselectivity of glycosylation are largely understood since chemical glycosylation was considered to be one of the useful methods to obtain glycosidic linkages as the alternative way of isolation from natural sources, strictly controlled formation of these 1,2- glycosides is generally difficult. This minireview introduces some of the recent advances in the development of 1,2- selective glycosylations, including the quite recent developments in glycosyl donor modification, reaction conditions, and methods for activation of intermolecular glycosylation, including the bimodal glycosylation strategy for 1,2- and 1,2- glycosides, as well as intramolecular glycosylations, including recent applications of NAP-ether-mediated intramolecular aglycon delivery.