THE EFFECT OF WATER ON THE CLAISEN REARRANGEMENT OF ALLYL VINYL ETHER- THEORETICAL METHODS INCLUDING EXPLICIT SOLVENT AND ELECTRON CORRELATION

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 polarisa tion of the solute is included in both treatments. In the continuum ca lculations these effects are included directly in the quantum mechanic al treatment, whilst in the classical simulations solute atomic charge s that reflect: both correlation and polarisation are employed. The re sults of the calculations are used to predict both the barrier lowerin g and the kinetic isotope effects in aqueous solution. The role of bot h electron correlation, solute polarisation and the need to include ex plicit solvent molecules are all clearly identified by the results pre sented.