S-腺苷甲硫氨酸依赖性烷基化反应：何时使用自由基反应？
S-Adenosylmethionine-dependent alkylation reactions: when are radical reactions used?
机构信息
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, United States.
出版信息
Bioorg Chem. 2011 Dec;39(5-6):161-70. doi: 10.1016/j.bioorg.2011.06.001. Epub 2011 Jun 28.
Abstract
S-Adenosylmethionine (SAM) is a versatile small molecule used in many biological reactions. This review focuses on the mechanistic consideration of SAM-dependent methylation and 3-amino-3-carboxypropylation reactions. Special emphasis is given to methylation and 3-amino-3-carboxypropylation of carbon atoms, for which both nucleophilic mechanisms and radical mechanisms are used, depending on the specific enzymatic reactions. What is the logic behind Nature's choice of different reaction mechanisms? Here I aim to rationalize the choice of different reaction mechanisms in SAM-dependent alkylation reaction by analyzing a few enzymatic reactions in depth. These reactions include SAM-dependent cyclopropane fatty acid synthesis, DNA cytosine methylation, RNA adenosine C2 and C8 methylation, and 3-amino-3-carboxypropylation involved in diphthamide biosynthesis and wybutosine biosynthesis.
摘要
S-腺苷甲硫氨酸（SAM）是一种在许多生物反应中广泛使用的多功能小分子。本综述重点介绍了依赖 SAM 的甲基化和 3-氨基-3-羧基丙基化反应的机制考虑。特别强调了碳原子的甲基化和 3-氨基-3-羧基丙基化，具体的酶促反应根据不同的碳原子需要用到亲核机制和自由基机制。那么，自然界选择不同反应机制的逻辑是什么呢？在这里，我通过深入分析几种酶促反应，旨在合理推断 SAM 依赖性烷基化反应中不同反应机制的选择。这些反应包括依赖 SAM 的环丙烷脂肪酸合成、DNA 胞嘧啶甲基化、RNA 腺苷 C2 和 C8 甲基化以及涉及二肽酰基生物合成和 wybutosine 生物合成的 3-氨基-3-羧基丙基化。
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