文献类型：期刊文献

英文题名：Promoter-Controlled Synthesis and Conformational Analysis of Cyclic Mannosides up to a 32-mer

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

年份：2023

卷号：62

期号：43

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20233014426535);WOS:【SCI-EXPANDED(收录号:WOS:001032228200001)】；

基金：Y Financial support from the National Natural Science Foundation of China (21871081, 22071054), the First-Class Discipline Construction and Characteristic Development Guidance Funds for the Central Universities (SLC13223002), the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission), Youth Innovation Promotion Association of CAS (2020258), and the Opening Project of Shanghai Key Laboratory of New Drug Design (21DZ2271600) is gratefully acknowledged. This study was supported by PRIN 2017 (2017XZ2ZBK, 2019-2023) to AS.

语种：英文

外文关键词：Carbohydrates; Conformational Analysis; Cyclic Oligosaccharides; Cycloglycosylation; Glycosylation

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.