Stereocontrolled 1,2-trans-arabinofuranosylation in the absence of 2-O-acyl group in glycosyl donor

IF 2.4 3区化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY

Carbohydrate Research Pub Date : 2024-08-30 DOI:10.1016/j.carres.2024.109252

Polina I. Abronina, Dmitry S. Novikov, Nelly N. Malysheva, Alexander I. Zinin, Alexander O. Chizhov, Leonid O. Kononov

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Abstract

Stereocontrolled 1,2-trans-α-arabinofuranosylation using polysilylated mono- and disaccharide glycosyl donors was investigated. A complete α-stereoselectivity of 1,2-trans-arabinofuranosylation was found for Ara-β-(1 → 2)-Ara disaccharide glycosyl donors containing five triisopropylsilyl (TIPS) groups with arylthiol (1) (as shown in our previous publications) or N-phenyltrifluoroacetimidoyl (2) (this work) leaving groups. Conversely, in case of monosaccharide thioglycosides polysilylated with acyclic silyl groups (TIPS, TBDPS), stereoselectivity of glycosylation was lower (α:β = 7–8:1), although the desired α-isomer still dominated. Disaccharide glycosyl donor 2 was successfully used in the synthesis of linear α-(1 → 5)-, β-(1 → 2)-linked hexaarabinofuranoside useful for further preparation of conjugates thereof as antigens valuable for the diagnosis of mycobacterioses.

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在糖基供体中没有 2-O-酰基的情况下进行立体控制的 1,2-反式阿拉伯呋喃糖基化反应

研究人员利用多硅烷基化的单糖和二糖糖基供体，对 1,2-反式-α-阿拉伯呋喃糖基化进行了立体控制。对于含有五个三异丙基硅烷基（TIPS）、带有芳基硫醇（1）（如我们以前的出版物所示）或 N-苯基三氟乙酰亚氨酰基（2）（本研究）离去基团的 Ara-β-(1 → 2)-Ara 二糖糖基供体，1,2-反式-阿拉伯呋喃糖基化具有完全的 α-严格选择性。相反，在单糖硫代糖苷与无环硅基（TIPS、TBDPS）聚合的情况下，糖基化的立体选择性较低（α:β = 7-8:1），但所需的α-异构体仍占主导地位。二糖糖基供体 2 成功用于合成线性 α-（1 → 5）-、β-（1 → 2）-连接的六阿拉伯呋喃糖苷，可进一步制备其共轭物，作为有价值的抗原用于分枝杆菌病的诊断。

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来源期刊

Carbohydrate Research 化学-生化与分子生物学

CiteScore

5.00

自引率

3.20%

发文量

183

审稿时长

3.6 weeks

期刊介绍： Carbohydrate Research publishes reports of original research in the following areas of carbohydrate science: action of enzymes, analytical chemistry, biochemistry (biosynthesis, degradation, structural and functional biochemistry, conformation, molecular recognition, enzyme mechanisms, carbohydrate-processing enzymes, including glycosidases and glycosyltransferases), chemical synthesis, isolation of natural products, physicochemical studies, reactions and their mechanisms, the study of structures and stereochemistry, and technological aspects. Papers on polysaccharides should have a "molecular" component; that is a paper on new or modified polysaccharides should include structural information and characterization in addition to the usual studies of rheological properties and the like. A paper on a new, naturally occurring polysaccharide should include structural information, defining monosaccharide components and linkage sequence. Papers devoted wholly or partly to X-ray crystallographic studies, or to computational aspects (molecular mechanics or molecular orbital calculations, simulations via molecular dynamics), will be considered if they meet certain criteria. For computational papers the requirements are that the methods used be specified in sufficient detail to permit replication of the results, and that the conclusions be shown to have relevance to experimental observations - the authors'' own data or data from the literature. Specific directions for the presentation of X-ray data are given below under Results and "discussion".