Plata, Robert Erik (2013-08). Experimental Observations in the Morita Baylis-Hillman Reaction in Methanol. Doctoral Dissertation.
Historically, research projects have originated from the literature group meetings and it was at one of those late night Wednesday meetings, nascent in my graduate career, that I presented a theoretical paper over the mechanism of the Morita Baylis-Hillman reaction. Something about it caught my attention and a project was born. The Morita Baylis-Hillman reaction had been heavily studied in the literature in recent years by both experimental and computational means. Some of these computational studies had even defined a complete theoretical mechanistic energy profile for these reactions. This dissertation describes a combination of experimental and theoretical mechanistic probes, including the observation of intermediates, the independent generation and partitioning of intermediates, thermodynamic and kinetic measurements for both the main reaction and interrelated side reactions, isotopic incorporation from solvent, and kinetic isotope effects, to fully define a more realistic picture of the free-energy profile for a Morita Baylis-Hillman reaction in methanol. Although the majority of this dissertation will be about the Morita Baylis-Hillman reaction in methanol, it could not have been fully accomplished without having to study the Morita Baylis-Hillman in DMSO and the Morita Baylis-Hillman utilizing acrylonitrile as well. All of these observations will be discussed.