The effect of water on the Claisen rearrangement of allyl vinyl ether: theoretical methods including explicit solvent and electron correlation

Abstract

The effect of water on the Claisen rearrangement of allyl vinyl ether is modelled using both ab initio continuum and Monte Carlo simulation techniques. The effect of electron correlation and electronic polarisation of the solute is included in both treatments. In the continuum calculations these effects are included directly in the quantum mechanical treatment, whilst in the classical simulations solute atomic charges that reflect both correlation and polarisation are employed. The results of the calculations are used to predict both the barrier lowering and the kinetic isotope effects in aqueous solution. The role of both electron correlation, solute polarisation and the need to include explicit solvent molecules are all clearly identified by the results presented.