Interaction of 2′-Deoxyadenosine
with <i>cis</i>-2-Butene-1,4-dial: Computational Approach
to Analysis
of Multistep Chemical Reactions
- Publication date
- Publisher
Abstract
The computational analysis of multistep chemical interactions
between
2′-deoxyadenosine and <i>cis</i>-2-butene-1,4-dial
has been performed. The applied protocol includes generation of a
multistep Gibbs free-energy reaction profile (PCM/M05-2X/6-311+G(d)
level) for the transformations of the reagents to products, followed
by evaluation of the rate constants, construction of the corresponding
kinetic equations, and solving them. Such a procedure allows one to
significantly extend the number of experimentally determined steps
by addition of the ones computationally predicted. The primary products
of the reaction are found to be four diastereomeric adducts characterized
by virtually the same stability. The acid-catalyzed dehydration of
these adducts leads to a more stable secondary product. Computational
verification of UV and NMR spectra has also been performed. It has
been revealed that simulated UV and NMR spectra of primary and secondary
2′-deoxyadenosine adducts of <i>cis</i>-2-butene-1,4-dial
are in agreement with the experimental observations
