Quantum chemical study of conformational preferences of intermediates and transition states in the alkaline hydrolysis of dimethyl phosphate

24th IUPAP Conference on Computational Physics

物理学;计算机科学

Takano, Y.^1 ; Kita, M.^1 ; Nakamura, H.^1

Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871, Japan^1

关键词: Alkaline hydrolysis;    Concerted reactions;    Conformational preferences;    Decomposition reaction;    Dimethyl phosphates;    Hydrolysis reaction;    Quantum chemical studies;    Reaction mechanism;   

Others  :  https://iopscience.iop.org/article/10.1088/1742-6596/454/1/012058/pdf
DOI  :  10.1088/1742-6596/454/1/012058

学科分类：计算机科学（综合）

来源: IOP

【 摘 要 】

The phosphate diester is a basic structure in DNA and RNA. The mechanism of phosphate diester hydrolysis is important for understanding the decomposition reactions of nucleic acids. In this study, we have explored the reaction pathway of alkaline hydrolysis of dimethyl phosphate, which is the simplest phosphate diester, with a hydroxide ion. Since the conformations of the intermediates and transition states reportedly influence the reaction mechanism of transacylation of methyl acetate with methoxide, we considered the conformational preferences on the alkaline hydrolysis of dimethyl phosphate, by using the most stable conformer as a reactant. Upon the reaction with hydroxide, a concerted reaction pathway was obtained in the gas phase, whereas a stepwise reaction pathway was obtained in water. As compared to the earlier study, our computation shows more stable conformations in the hydrolysis reactions than the previous study.