通过变色莫里塔-贝利斯-希尔曼加成途径制备光反应非天然 RNA 碱基

IF 3 4区 化学 Q3 CHEMISTRY, PHYSICAL
Dr. Matteo Lami, Dr. Leonardo Barneschi, Dr. Mario Saletti, Prof. Dr. Massimo Olivucci, Prof. Dr. Andrea Cappelli, Prof. Dr. Marco Paolino
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引用次数: 0

摘要

基于 RNA 的生物学和药理学研究工具正引起越来越多的关注。其中,可通过特定波长的光照控制生物活性的 RNA 合体是一个重要目标。在此,我们报告了一项原理验证研究,该研究支持系统地利用莫里塔-贝利斯-希尔曼加合物(MBHAs)合成光响应 RNA 构建模块的可行性。因此,在对四种天然 RNA 碱基以及两种非天然碱基(5-氨基甲基尿嘧啶和 5-甲基氨基甲基尿嘧啶)进行功能化时,使用了一种特定的乙酰化 MBHA 衍生物。结果表明,这两种非天然碱基的官能化具有高度选择性。随后对共轭产物进行了光谱、光化学和计算研究。结果表明,当存在单个光响应单元时(即使用 5-甲基氨基甲基尿嘧啶),生成的非天然尿嘧啶就像一个基于肉桂酸框架的光化学开关,在光照下通过生物模拟光诱导的分子内电荷转移机制驱动无障碍的超快反应路径发生异构化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Preparation of Light-responsive Unnatural RNA Bases via a Chromogenic Morita-Baylis-Hillman Adduct Path

Preparation of Light-responsive Unnatural RNA Bases via a Chromogenic Morita-Baylis-Hillman Adduct Path

RNA-based tools for biological and pharmacological research are raising an increasing interest. Among these, RNA aptamers whose biological activity can be controlled via illumination with specific wavelengths represent an important target. Here, we report on a proof-of-principle study supporting the viability of a systematic use of Morita-Baylis-Hillman adducts (MBHAs) for the synthesis of light-responsive RNA building blocks. Accordingly, a specific acetylated MBHA derivative was employed in the functionalization of the four natural RNA bases as well as two unnatural bases (5-aminomethyl uracil and 5-methylaminomethyl uracil). The results reveal a highly selective functionalization for both unnatural bases. The conjugation products were then investigated spectroscopically, photochemically and computationally. It is shown that when a single light-responsive unit is present (i. e. when using 5-methylaminomethyl uracil), the generated unnatural uracil behaves like a cinnamic-framework-based photochemical switch that isomerizes upon illumination through a biomimetic light-induced intramolecular charge transfer mechanism driving a barrierless and, therefore, ultrafast reaction path.

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来源期刊
ChemPhotoChem
ChemPhotoChem Chemistry-Physical and Theoretical Chemistry
CiteScore
5.80
自引率
5.40%
发文量
165
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