�On water� reactions have recently been observed to experience enhanced rates, yields, and specificity for many organic reactions compared to traditional methods.  A novel QM/MM Monte Carlo, free-energy perturbation methodology was developed for accurately predicting the rate accelerations at the aqueous interface.  The reactions of interest were the Claisen rearrangements of allyl p-R-phenyl ether (R = CH3, OCH3, and Br) and allyl naphthyl ether in an �on water� environment and 15 other solvents and the Aldol reaction of benzaldehyde and acetone with a chiral organocatalyst.   An explanation of the enhancements seen by �on water� reactions will be showcased and will involve the discussion of radial distribution functions, solute-solvent energy pair distributions, hydrophobic effects, solvent polarizability and the orientation and position of the aromatic ethers at the aqueous interface.

Development of “on water” QM/MM methodology for the Claisen rearrangement of allyl <i>p</i>-R-phenyl ethers and allyl naphthyl ether and Aldol reaction of benzaldehyde and acetone with a chiral organocatalyst

245th National Meeting (2013)

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Development of “on water” QM/MM methodology for the Claisen rearrangement of allyl p-R-phenyl ethers and allyl naphthyl ether and Aldol reaction of benzaldehyde and acetone with a chiral organocatalyst