Fleming Aaron M, Alshykhly Omar, Orendt Anita M, Burrows Cynthia J
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850, USA.
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850, USA ; Center for High Performance Computing, University of Utah, Salt Lake City, Utah 84112-0190, USA.
Tetrahedron Lett. 2015 Jun 3;56(23):3191-3196. doi: 10.1016/j.tetlet.2014.12.052.
Oxidation of the guanine heterocycle by two electrons can yield the chiral product 5-carboxamido-5-formamido-2-iminohydantoin (). The free base enantiomers were synthesized from 2'-deoxyguanosine oxidized with a Cu(II)/HO oxidant system followed by hydrolysis of the -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.
鸟嘌呤杂环经双电子氧化可生成手性产物5-羧酰胺基-5-甲酰胺基-2-亚氨基乙内酰脲（）。游离碱对映体由2'-脱氧鸟苷经Cu(II)/HO氧化体系氧化，随后糖苷键水解合成。通过电子圆二色光谱对这些异构体进行了研究，以确定它们的绝对构型。在气相和溶剂模拟条件下完成了预期光谱的含时密度泛函理论计算，以便解释实验光谱并给出绝对构型归属。
