We have studied a set of ketal Claisen rearrangements that have the possibility of producing three different regioisomeric and diastereomeric products through a total of 6 distinct transition state topologies. These pathways, however, cannot be differentiated under experimental conditions. By comparing experimental data to theoretical results based on Density Functional Theory, we probe the various pathways by studying the relative activation energies of the 6 different transition states. Our results will help us to not only calibrate current DFT methods but also understand the energetics of reaction pathways that may not be measured experimentally. We are using theoretical methods that have been previously shown to accurately treat relative activation energies in amide acetal Claisen rearrangements. We present results from the M06-2X functional and the 6-31+g(d,p) basis set. We also compare with Random Phase Approximation results for these systems, which have been shown previously to be useful in understanding the kinetics of related reactions.

Experimental and theoretical analysis of relative activation energies of various ketal Claisen rearrangements

251st National Meeting (2016)

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