6-arylpurine 核糖核苷和 2'-脱氧核糖核苷的嘌呤 N 定向酰基化及机理研究。

IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC
Mahesh K Lakshman, Casina T Malinchak, Nathaniel Shank, Michelle C Neary, Lothar Stahl
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引用次数: 0

摘要

嘌呤环含有四个不同碱性的嵌入氮原子。选择性地利用这些环上的氮原子,可以相对容易地实现远程功能化,从而获得不易获得的修饰嘌呤基基团。在此,我们报告了以前未曾描述过的 6-芳基嘌呤核糖核苷和更易变的 2'-脱氧核糖核苷的 N-定向芳基化。动力学同位素分析以及与定义明确的二聚、苍白球化 9-苄基 6-芳基嘌呤的反应证明,N-定向环金属化是一个关键步骤,具有可信的限速 C-H 键裂解。自由基抑制实验表明,可能存在芳基自由基中间体。这种化学方法克服了多氮化和多氧核苷酸结构功能化过程中经常遇到的困难,这些核苷酸结构具有复杂的反应活性和易变的糖苷键,在 2'- 脱氧底物中更为敏感。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Purinyl <i>N</i>-directed aroylation of 6-arylpurine ribo- and 2'-deoxyribonucleosides, and mechanistic insights.

Purinyl N-directed aroylation of 6-arylpurine ribo- and 2'-deoxyribonucleosides, and mechanistic insights.

The purinyl ring contains four embedded nitrogen atoms of varying basicities. Selective utilization of these ring nitrogen atoms can lead to relatively facile remote functionalization, yielding modified purinyl motifs that are otherwise not easily obtained. Herein, we report previously undescribed N-directed aroylation of 6-arylpurine ribo and the more labile 2'-deoxyribonucleosides. Kinetic isotope analysis as well as reaction with a well-defined dimeric, palladated 9-benzyl 6-arylpurine provided evidence for N-directed cyclometallation as a key step, with a plausible rate-limiting C-H bond cleavage. Radical inhibition experiments indicate the likely intermediacy of aroyl radicals. The chemistry surmounts difficulties often posed in the functionalization of polynitrogenated and polyoxygenated nucleosidic structures that possess complex reactivities and a labile glycosidic bond that is more sensitive in the 2'-deoxy substrates.

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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: The international home of synthetic, physical and biomolecular organic chemistry.
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