We applied Density Functional Theory and the recently developed DFT-based RPA Method of Furche and coworkers to study substituent effects in the amide-acetal Claisen rearrangement. We examined the reactions of amide acetals of 5- and 6-membered ring structures with allylic alcohols with varying substituents, such as propyl and phenyl groups, and calculated relative transition state energy and free energy differences to predict product distributions. We compared our theoretical results with experimental transition state free energy differences. In agreement with experiment, our results predict that the syn chair-like conformations of the transition states (which produce the <i>syn</i> product) are favored over the boat-like conformations (which produce the <i>anti</i> product). In order to validate our theoretical results we examined a variety of methods (B3LYP, M06-2X, MP2, MP4, RPA) and basis sets (6-31G(d), cc-PVDZ, cc-PVTZ) and compared predictions from these methods. We discuss the implications of these results and future targets for study.

Density functional theory treatment of substituent effects on the amide-acetal Claisen rearrangement

249th National Meeting (2015)

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