A Theoretical study of hexanediol dehydration reaction

Shiga, Motoyuki   

In recent years, the use of high-temperature water as a reaction field is being actively discussed in the field of green chemistry. A novel approach from theoretical and computational chemistry is expected to play the important part in its basic understanding, e.g. how the water molecules are involved in the reactions. For this aim we study herein one of the prototypical reactions, 2,5-hexanediol dehydration, which is known as a promising way for the conversion of biomass-derived polyalcohols using the high temperature carbonated water. To clarify the whole reaction mechanism we carried out three different ab initio simulations; we used string method to extract the reaction coordinate, metadynamics to calculate the free energy landscape, and molecular dynamics to explore the trajectory in real time.