Computational studies of electronic circular dichroism spectra predict absolute configuration assignments for the guanine oxidation product 5-carboxamido-5-formamido-2-iminohydantoin
Computational studies of electronic circular dichroism spectra predict absolute configuration assignments for the guanine oxidation product 5-carboxamido-5-formamido-2-iminohydantoin
复制标题
DOI：
10.1016/j.tetlet.2014.12.052
复制
发表时间：
2015-06-03
影响因子：
1.8
通讯作者：
Burrows, Cynthia J.
中科院分区：
文献类型：
--
作者：
Fleming, Aaron M.;Alshykhly, Omar;Burrows, Cynthia J.
鸟嘌呤杂环被两个电子氧化可产生手性产物5-甲酰胺基-5-甲酰胺基-2-亚氨基乙内酰脲（2 Ih）。用Cu（II）/H2 O2氧化剂体系氧化2 ′-脱氧鸟苷，然后水解N-糖苷键，合成2 Ih游离碱对映体。这些异构体分别研究了电子圆二色光谱测定其绝对构型。在气相和溶剂建模中完成了对预期光谱的时间依赖密度泛函理论计算，以解释实验光谱并提供绝对构型分配。(C)2014爱思唯尔有限公司版权所有。
Oxidation of the guanine heterocycle by two electrons can yield the chiral product 5-carboxamido-5-formamido-2-iminohydantoin (2Ih). The 2Ih free base enantiomers were synthesized from 2'-deoxyguanosine oxidized with a Cu(II)/H2O2 oxidant system followed by hydrolysis of the N-glycosidic bond. These isomers were each studied by electronic circular dichroism spectroscopy for determination of their absolute configurations. Time-dependent density functional theory calculations of the expected spectra were completed in both the gas phase and with solvent modeling in order to interpret the experimental spectra and provide the absolute configuration assignments. (C) 2014 Elsevier Ltd. All rights reserved.