Total Synthesis of Nona-decasaccharide Motif from Ganoderma sinense Polysaccharide Enabled by Modular and One-Pot Stereoselective Glycosylation Strategy

doi:10.1021/jacs.4c05188

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	Total Synthesis of Nona-decasaccharide Motif from Ganoderma sinense Polysaccharide Enabled by Modular and One-Pot Stereoselective Glycosylation Strategy
	Chen, Zhiyuan; Xiao, Guozhi
	2024
发表期刊	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN	0002-7863
卷号	146 期号:25 页码:17446-17455
摘要	Polysaccharides from a medicinal fungus Ganoderma sinense represent important and adjunctive therapeutic agents for treating various diseases, including leucopenia and hematopoietic injury. However, the synthetic accessibility to long, branched, and complicated carbohydrates chains from Ganoderma sinense polysaccharides remains a challenging task in chemical synthesis. Here, we report the modular chemical synthesis of nona-decasaccharide motif from Ganoderma sinense polysaccharide GSPB70-S with diverse biological activities for the first time through one-pot stereoselective glycosylation strategy on the basis of glycosyl ortho-(1-phenyvinyl)benzoates, which not only sped up carbohydrates synthesis but also reduced chemical waste and avoided aglycones transfer issues inherent to one-pot glycosylation on the basis of thioglycosides. The synthetic route also highlights the following key steps: (1) preactivation-based one-pot glycosylation for highly stereoselective constructions of several 1,2-cis-glycosidic linkages, including three alpha-d-GlcN-(1 -> 4) linkages and one alpha-d-Gal-(1 -> 4) bond via the reagent N-methyl-N-phenylformamide modulation; (2) orthogonal one-pot assembly of 1,2-trans-glycosidic linkages in various linear and branched glycans fragments by strategic combinations of glycosyl N-phenyltrifluoroacetimidates, glycosyl ortho-alkynylbenzoates, and glycosyl ortho-(1-phenyvinyl)benzoates; and (3) the final [1 x 4 + 15] Yu glycosylation for efficient assembly of nona-decasaccharide target. Additionally, shorter sequences of 4-mer, 5-mer, and 6-mer are also prepared for structure-activity relationship biological studies. The present work shows that this one-pot stereoselective glycosylation strategy can offer a reliable and effective means to streamline chemical synthesis of long, branched, and complex carbohydrates with many 1,2-cis-glycosidic bonds.
DOI	10.1021/jacs.4c05188
WOS记录号	WOS:001246454500001
引用统计
文献类型	期刊论文
条目标识符	http://ir.kib.ac.cn/handle/151853/76007
专题	中国科学院昆明植物研究所
推荐引用方式 GB/T 7714	Chen, Zhiyuan,Xiao, Guozhi. Total Synthesis of Nona-decasaccharide Motif from Ganoderma sinense Polysaccharide Enabled by Modular and One-Pot Stereoselective Glycosylation Strategy[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(25):17446-17455.
APA	Chen, Zhiyuan,&Xiao, Guozhi.(2024).Total Synthesis of Nona-decasaccharide Motif from Ganoderma sinense Polysaccharide Enabled by Modular and One-Pot Stereoselective Glycosylation Strategy.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(25),17446-17455.
MLA	Chen, Zhiyuan,et al."Total Synthesis of Nona-decasaccharide Motif from Ganoderma sinense Polysaccharide Enabled by Modular and One-Pot Stereoselective Glycosylation Strategy".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.25(2024):17446-17455.

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