UV-mediated anomeric activation

IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC
Niklas Henrik Fischer, Alicja Klaudia Bałuta, Maciej Tadeusz Szpak, Peter Waaben Thulstrup and Christian Marcus Pedersen
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引用次数: 0

Abstract

We report the UV-mediated activation of various glycosyl α-trichloroacetimidates (TCAs) to form glycosyl α-chlorides or O-glycosides depending on the carbohydrate, protecting groups, and solvent. In THF, Et2O, and CH2Cl2, most of the glycosyl TCAs studied underwent conversion to their respective α-chlorides. In the case of per-acetylated glucosyl TCA, a reaction with THF was observed which caused formation of the 4′-chlorobutyl β-glucoside. O-Glycosylation with primary and secondary alcohols present in large excess was found to take place in acetonitrile, which was chosen as solvent because it does not facilitate competing glycosyl chloride formation. Fluorescent byproducts were formed in THF, Et2O, and in reactions with benzyl-protected TCAs. We propose that this is a result of decomposition of 2,3-dichloromaleimide formed from eliminated trichloroacetamide via a series of radical reactions.

Abstract Image

紫外线介导的异构体活化。
我们报道了紫外线介导的各种糖基α-三氯乙酸酯(TCAs)的活化,根据碳水化合物、保护基团和溶剂形成糖基α-氯化物或o -糖苷。在THF、Et2O和CH2Cl2中,研究的大多数糖基TCAs转化为各自的α-氯化物。在过乙酰化葡萄糖基TCA的情况下,观察到与四氢呋喃的反应导致4'-氯丁基β-葡萄糖苷的形成。在乙腈中发现大量过量的伯醇和仲醇的o -糖基化发生,选择乙腈作为溶剂是因为它不促进竞争氯代糖基的形成。在THF、Et2O和与苯基保护的TCAs反应中形成荧光副产物。我们认为这是由消除的三氯乙酰胺通过一系列自由基反应生成的2,3-二氯马来酰亚胺分解的结果。
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来源期刊
Organic & Biomolecular Chemistry
Organic & Biomolecular Chemistry 化学-有机化学
CiteScore
5.50
自引率
9.40%
发文量
1056
审稿时长
1.3 months
期刊介绍: Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.
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