Stereoselective Synthesis of 2-Deoxythiosugars from Glycals

You, Xueying; Cai, Yi; Xiao, Chenyu; Ma, Lijuan; Wei, Yong; Xie, Tianpeng; Chen, Lei; Yao, Hui

doi:10.3390/molecules27227979

Cited by 6 publications

(2 citation statements)

References 39 publications

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“…根据相关文献方法 [38][39] , 将天然产物中的羟基酯化、偶联并水解为巯基, 分别得到了雌酮和姜酮的硫酚类似物. 随后, 本方法以这些天然产物的硫酚类似物为亲核试剂, 在 Pd 2 (dba) 3 催化下与 6-膦酸酯-3,4-碳酸酯 a All reactions were carried out with 5 mol% zinc dust, 5 mol% Ni catalyst, 10 mol% ligand in 2 mL of MeCN, which was stirred at 80 ℃ for 5 h under N 2 atmosphere.…”

Section: 天然产物的 1-/3-硫糖基化修饰mentioning

confidence: 99%

Regio- and Stereo-selective Synthesis of 1β-/3R-Aryl Thiosugar

Zou,

Wang,

Yao

et al. 2024

Chinese Journal of Organic Chemistry

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Thiosugars have attracted much attention in the field of pharmaceuticals because of their excellent biological activities, and chemical synthesis is an important way to obtain thiosugars. Using 6-O-diphenylphosphoryl-3,4-O-carbonate-D-galactal and thiophenols as starting materials, the regio-and stereo-selective syntheses of 1β-/(3R)-aryl thiosugars were controlled with NiBr2 and Pd2(dba)3 catalysts, respectively. The structures of the target compounds were characterized by nuclear magnetic resonance, high-resolution mass spectrometry and single crystal X-ray diffraction. This method exhibited favourable compatibility with various functional groups substituted thiophenols, which could be used for the structural modification of active natural products. The research work is help for the rapid construction of the compound library of 1β-/(3R)-aryl thiosugars for drug discovery. Keywords Pd catalysis; Ni catalysis; D-galactal; thiosugar; synthesis 近年来, 糖类化合物作为生物成像的载体 [1] 、修饰 DNA 和蛋白质的重要物质 [2] 和细胞培养保存的介质 [3] , 在生物领域被广泛研究. 硫代糖类化合物作为氧糖苷的类似物, 具有更广泛的生物活性和更好的稳定性. 细胞表面的一些糖类承担着免疫识别的重要作用, 硫代糖已经被证明是酶系统中碳水化合物与蛋白质之间相互作用的重要工具 [4] . 硫代低聚糖 S-Galp(α1→3)Galp 还可作为在锥形虫细胞表面被溶菌抗体识别的拟糖 [5] (图 1). 药物和天然产物的糖基化修饰具有重要意义 [6][7] , 例如 3-硫代糖修饰的蛋白质可有效应用于细胞标记 [8][9] ; 胰高血糖素样态 1 (GLP-1)经过硫代糖的修饰后, 其生物活性和抗酶解性都得到了显著的提升 [10] ; 硫代糖类能用于治疗糖尿病 [11] 和调控植物细胞代谢 [12] . 此外, 硫代糖还作为合成低聚寡糖的重要中间体而被广泛研究 [13][14] . 许多已在市售或正在研发中的硫代糖类药物, 如金诺芬 (Auranfin) [15][16][17] 、芸苔葡糖硫苷(Glucosinolate) [18][19][20] 和吡利霉素(Pirlimycin) [21][22] 等(图 1)展现出了抗风湿炎症、抗癌特性及治疗神经系统疾病等效果.

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Section: 天然产物的 1-/3-硫糖基化修饰mentioning

confidence: 99%

Regio- and Stereo-selective Synthesis of 1β-/3R-Aryl Thiosugar

Zou,

Wang,

Yao

et al. 2024

Chinese Journal of Organic Chemistry

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“…Most S -glycosylation reactions were developed with saturated glycosyl donors, and the stereoselectivity typically relied on the original anomeric configuration prepared in advance . With the development of olefin chemistry, unsaturated glycosyl donors (glycals) were also widely applied in synthesizing S -glycosides . As shown in Scheme a, the conventional S -glycosylation of glycal donors and S -nucleophiles was promoted by Brønsted/Lewis acids through allylic oxycarbenium ion intermediate (Ferrier rearrangement), generating α-2,3-unsaturated S -glycosides as the main products .…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Synthesis of β-S-Glycosides via Palladium Catalysis

Liu,

Wang,

Chen

et al. 2024

J. Org. Chem.

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S-Glycosides are more resistant to enzymatic and chemical hydrolysis and exhibit higher metabolic stability than common O-glycosides, demonstrating their widespread application in biological research and drug development. In particular, β-Sglycosides are used as antirheumatic, anticancer, and antidiabetic drugs in clinical practice. However, the stereoselective synthesis of β-S-glycosides is still highly challenging. Herein, we report an effective β-S-glycosylation using 3-O-trichloroacetimidoyl glycal and thiols under mild conditions. The C3-imidate is designed to guide Pd to form a complex with glucal from the upper face, followed by Pd−S (thiols) coordination to realize β-stereoselectivity. This method demonstrates excellent compatibility with a broad scope of various thiol acceptors and glycal donors with yields up to 87% and a β/α ratio of up to 20:1. The present β-S-glycosylation strategy is used for late-stage functionalization of drugs/natural products such as estrone, zingerone, and thymol. Overall, this novel and simple operation approach provides a general and practical strategy for the construction of β-thioglycosides, which holds high potential in drug discovery and development.

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One‐Pot Stereoselective Synthesis of 2,3,4‐Unprotected β‐N‐Glycopyranosides from Glycals and Amines

Gao

Wang

et al. 2023

Adv Synth Catal

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A one‐pot synthesis of 2,3,4‐unprotected β‐N‐glycopyranosides from glycals and amines with exclusive β‐stereoselectivity under room temperature conditions is reported. This method was achieved via palladium‐catalyzed Tsuji‐Trost amination followed by dihydroxylation directly, tolerating anilines, heterocyclic aromatic amines, and N,O‐dimethylhydroxylamine, especially the reaction of primary amines and glycals has not been reported before. Furthermore, the protocol was applied to modify clinical drugs (prazosin, imiquimod) and construct the analogue of the natural product amphimedoside A.

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Stereoselective Synthesis of 2-Deoxythiosugars from Glycals

Cited by 6 publications

References 39 publications

Regio- and Stereo-selective Synthesis of 1β-/3R-Aryl Thiosugar

Regio- and Stereo-selective Synthesis of 1β-/3R-Aryl Thiosugar

Stereoselective Synthesis of β-S-Glycosides via Palladium Catalysis

One‐Pot Stereoselective Synthesis of 2,3,4‐Unprotected β‐N‐Glycopyranosides from Glycals and Amines

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