Abstract
Free energy of solvation profiles for the Diels-Alder reaction of cyclopentadiene and methyl vinyl ketone have been obtained in liquid propane, methanol, and water at 25 °C. Four transition states were located for the gas-phase reaction from ab initio calculations with the 3–21G and 6–31G(d) basis sets. Calculations at the MP3/6–31G(d)//6–31G(d) level confirmed that the endo-cis transition state is lowest in energy. The gas-phase minimum energy reaction path was followed in periodic cells containing 260-500 solvent molecules in Monte Carlo simulations, which yielded the changes in free energies of solvation. Essentially no solvent effect was found in propane; however, hydration is computed to lower the free energy of activation by 4.2 ± 0.4 kcal/mol, similar to experimental observations. Intermediate effects are computed and observed for methanol. The rate accceleration in water is traced to both a hydrophobic effect and enhanced hydrogen bonding to the carbonyl group in the transition state.
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Jorgensen, W.L., Lim, D., Blake, J.F. (1993). Solvent Effects on the Diels-Alder Reaction of Methyl Vinyl Ketone and Cyclopentadiene from Computer Simulations. In: Joyner, R.W., van Santen, R.A. (eds) Elementary Reaction Steps in Heterogeneous Catalysis. NATO ASI Series, vol 398. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-1693-0_23
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DOI: https://doi.org/10.1007/978-94-011-1693-0_23
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