Theoretical studies of the hydrolysis reaction of 5′‐AMP

The hydrolysis reaction mechanisms of the phosphate group, with and without an adenosine connected to it, have been theoretically investigated at the B3LYP/6‐31G** level. It is found that each reaction is single‐channel with a two‐step process. When H₂O approaches the phosphate group, a penta‐coordinated intermediate (IM1‐a) is formed first, followed by the H transfer reaction with P? O broken at the same time. This process belongs to the addition‐elimination process, similar to the carboxylate. In addition, the solvent effect has been studied by the polarizable continuum model (PCM). Our present calculations have rationalized and verified all the possible reaction channels. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006