Promoter-Controlled Synthesis and Conformational Analysis of Cyclic Mannosides up to a 32-mer

被引：11

作者：

Li, Xiaona ^{[1
]}

Di Carluccio, Cristina ^{[2
]}

Miao, He ^{[1
]}

Zhang, Lvfeng ^{[1
]}

Shang, Jintao ^{[1
]}

Molinaro, Antonio ^{[2
,3
]}

Xu, Peng ^{[4
]}

Silipo, Alba ^{[2
,3
]}

Yu, Biao ^{[4
]}

Yang, You ^{[1
]}

机构：

[1] East China Univ Sci & Technol, Shanghai Frontiers Sci Ctr Optogenet Tech Cell Met, Engn Res Ctr Pharmaceut Proc Chem, Sch Pharm,Shanghai Key Lab New Drug Design,Minist, 130 Meilong Rd, Shanghai 200237, Peoples R China

[2] Univ Naples Federico II, Dept Chem Sci, Via Cintia 4, I-80126 Naples, Italy

[3] Osaka Univ, Sch Sci, Dept Chem, 1-1 Osaka Univ Machikaneyama, Toyonaka, Osaka 5600043, Japan

[4] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Bioorgan & Nat Prod Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 43期

基金：

中国国家自然科学基金;

关键词：

Carbohydrates; Conformational Analysis; Cyclic Oligosaccharides; Cycloglycosylation; Glycosylation; CHEMICAL-SYNTHESIS; GLUCAN SYNTHESIS; GLYCOSYLATION; CYCLODEXTRINS; TETRASACCHARIDES; OLIGOSACCHARIDES; RELEVANT;

D O I：

10.1002/anie.202307851

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cyclodextrins are widely used as carriers of small molecules for drug delivery owing to their remarkable host properties and excellent biocompatibility. However, cyclic oligosaccharides with different sizes and shapes are limited. Cycloglycosylation of ultra-large bifunctional saccharide precursors is challenging due to the constrained conformational spaces. Herein we report a promoter-controlled cycloglycosylation approach for the synthesis of cyclic & alpha;-(1 & RARR;6)-linked mannosides up to a 32-mer. Cycloglycosylation of the bifunctional thioglycosides and (Z)-ynenoates was found to be highly dependent on the promoters. In particular, a sufficient amount of a gold(I) complex played a key role in the proper preorganization of the ultra-large cyclic transition state, providing a cyclic 32-mer polymannoside, which represents the largest synthetic cyclic polysaccharide to date. NMR experiments and a computational study revealed that the cyclic 2-mer, 4-mer, 8-mer, 16-mer, and 32-mer mannosides adopted different conformational states and shapes.

引用

页数：8

共 55 条

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[2]

[Anonymous], 2009, ANGEW CHEM, V121, P1932

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