Deconvoluting the reactivity of two intermediates formed from modified pyrimidines.
Deconvoluting the reactivity of two intermediates formed from modified pyrimidines.
复制标题
对由修饰嘧啶形成的两个中间体的反应性进行解卷积。
DOI：
10.1021/ol401472m
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发表时间：
2013
期刊：
影响因子：
5.2
通讯作者：
Greenberg,MarcM
中科院分区：
文献类型：
--
作者：
Weng,Liwei;Horvat,SoniaM;Schiesser,CarlH;Greenberg,MarcM
重新检查了5-（2′-脱氧尿苷基）甲基自由基（6）的产生。经4-羟基-2，2，6，6-四甲基哌啶-1-氧自由基捕获证实生成了6。然而，通过甲氧基胺的捕获揭示了也产生了相应的碳阳离子（10）。检查这些陷阱对DNA产物的影响，发现碳阳离子和非6产生链间交联。从碳阳离子的交联形成是一致的DFT计算预测，除了在N1位置的DA基本上是无势垒的。
Generation of the 5-(2′-deoxyuridinyl)methyl radical (6) was reexamined. Trapping by 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl confirms that6is generated. However, trapping by methoxyamine reveals that the respective carbocation (10) is also produced. Examining the effects of these traps on products in DNA reveals that the carbocation and not6yields interstrand cross-links. Cross-link formation from the carbocation is consistent with DFT calculations that predict that addition at the N1 position of dA is essentially barrierless.