Transfer Hydrogenation in Open-Shell Nucleotides — A Theoretical Survey

Molecules

Florian Achrainer²  Hendrik Zipse¹  John C. Walton² 

[1] id="af1-molecules-19-21489">Department of Chemistry, Ludwig-Maximilians-Universität Munich, Butenandtstr. 5–13, Munich 81377, Germa

关键词: transfer hydrogenation;    open-shell nucleotides;    thermochemistry;    heats of hydrogenation;    radical stabilization energy;   

DOI  :  10.3390/molecules191221489

来源: mdpi

【 摘 要 】

The potential of a larger number of sugar models to act as dihydrogen donors in transfer hydrogenation reactions has been quantified through the calculation of hydrogenation energies of the respective oxidized products. Comparison of the calculated energies to hydrogenation energies of nucleobases shows that many sugar fragment radicals can reduce pyrimidine bases such as uracil in a strongly exothermic fashion. The most potent reducing agent is the C3' ribosyl radical. The energetics of intramolecular transfer hydrogenation processes has also been calculated for a number of uridinyl radicals. The largest driving force for such a process is found for the uridin-C3'-yl radical, whose rearrangement to the C2'-oxidized derivative carrying a dihydrouracil is predicted to be exothermic by 61.1 kJ/mol in the gas phase.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.