半乳糖基化的立体化学结果受远端酰基保护基的位置和吸电子能力的影响。

IF 3.6 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry Pub Date : 2025-05-08 DOI:10.1021/acs.joc.4c02956

Line Juul-Madsen,Nikolai Cordua,Rasmus D Greve,Kamilla Pedersen,Helle H Trinderup,Elena Petersen,Henrik H Jensen

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引用次数: 0

摘要

研究了不同远端苯甲酰酯对半乳糖酰基化反应的定向作用。结果表明，半乳糖基苯基硫甙型给体的O-6上的酯对其选择性的影响可以忽略不计。相反，4- o -苯甲酰、3,4-二- o -苯甲酰和4,6-二- o -苯甲酰保护的半乳糖给体发生了α-选择性半乳糖基化，其中高吸电子性的对硝基苯甲酰（pNO2Bz）保护基团提供了最具α-选择性的半乳糖基化。此外，用高活性的环己基糖基取代噻吩基糖基可以提高α-选择性。这些发现使得生物学相关的α-d-Gal(1→4)Gal连锁得以成功合成。所获得的结果不建议远端参与的过程中观察到的球头选择性。

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The Stereochemical Outcome of Galactosylations Is Influenced by Both the Position and Electron-Withdrawing Power of Distal Acyl Protecting Groups.

The stereodirecting effect of various distal benzoyl esters on the anomeric selectivity in galactopyranosylations was investigated. It was found that esters on O-6 of galactosyl donors of the phenyl thioglycoside type had a negligible influence on the anomeric selectivity. Instead, α-selective galactosylations were observed with 4-O-benzoyl, 3,4-di-O-benzoyl, and 4,6-di-O-benzoyl protected galactosyl donors, with the highly electron-withdrawing p-nitrobenzoyl (pNO2Bz) protecting group providing the most α-selective galactosylations. Furthermore, the α-selectivity was enhanced by replacing the thiophenyl aglycon functionality with the highly reactive cyclohexyl aglycon functionality. These findings enabled the successful synthesis of the biologically relevant α-d-Gal(1→4)Gal linkage. The obtained results do not suggest distal participation as a course for the observed anomeric selectivities.

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来源期刊

Journal of Organic Chemistry 化学-有机化学

CiteScore

6.20

自引率

11.10%

发文量

1467

审稿时长

2 months

期刊介绍： Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.