Time-Resolved Spectroscopic Observation of Diphenylnitrenium Ion Reactions with Guanosine.,The Journal of Organic Chemistry

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Time-Resolved Spectroscopic Observation of Diphenylnitrenium Ion Reactions with Guanosine.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-06-12 , DOI: 10.1021/acs.joc.0c00517
Lili Du _{1,

2} , Zhiping Yan _{1,

3} , Zhiyuan Zhu ₁ , Shun-Cheung Cheng ₁ , Yue Zhang ₁ , Xuechen Li ₁ , Wenjian Tang ₄ , David Lee Phillips ₁

Affiliation

Arylnitrenium ions have gained attention for their high reactivity toward guanosine, which in some cases has been linked to carcinogenesis. Although many studies have examined covalent addition reactions between arylnitrenium ions and guanosine, there is still some uncertainty regarding the attack position of nitrenium ions on guanosine and its derivatives. In this paper, we employ nanosecond transient absorption and nanosecond time-resolved resonance Raman spectroscopy to investigate the reaction between the N,N-di(4-bromophenyl) nitrenium ion (2) and guanosine. Our time-resolved spectroscopic results and photochemical product analysis results show that the reaction of guanosine with 2 generates an N7 intermediate that subsequently undergoes rearrangement and deprotonation to produce a C8 adduct. Comparing these results to our previous study between the 2-fluorenylnitrenium ion and guanosine indicates that the structure and properties of arylnitrenium ions are able to influence the reaction pathways and intermediate structures.

中文翻译：

时间分辨光谱观察的鸟嘌呤二苯基氮离子反应。

芳基氮离子对鸟嘌呤的高反应性引起人们的关注，在某些情况下鸟嘌呤与致癌作用有关。尽管许多研究已经研究了芳基氮化物离子和鸟苷之间的共价加成反应，但关于硝化氮离子对鸟苷及其衍生物的攻击位置仍然存在一些不确定性。在本文中，我们使用纳秒瞬态吸收和纳秒时间分辨共振拉曼光谱研究N，N-二（4-溴苯基）ion离子（2）与鸟苷之间的反应。我们的时间分辨光谱结果和光化学产物分析结果表明，鸟苷与2的反应生成N7中间体随后经过重排和去质子化产生C8加合物。将这些结果与我们先前在2-芴基氮离子和鸟嘌呤之间的研究进行比较表明，芳基氮离子的结构和性质能够影响反应途径和中间结构。

更新日期：2020-07-17

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