The interactions between Lewis acids and carbonyls have played a significant role in the construction of important molecules. While a great deal of insight has been gained regarding classical stoichiometric regimes, more discoveries continue to be made about the complexities of these interactions between carbonyls and Lewis acids in catalytic systems. In particular, the new reactivity observed in Lewis acid-catalyzed carbonyl-olefin metathesis demonstrates that a comprehensive understanding of the interactions between these classical Lewis pairs remains incomplete. It is our hypothesis that the application of in situ techniques will provide key insights into reactivity initiated by the interactions of Lewis pairs that are as yet unexplored. Synthetic, spectroscopic, kinetic, and computational techniques will be presented which facilitate characterization of both the ground and transition state behavior of Lewis acids and carbonyl compounds. These data will be used to demonstrate the complex interplay of Lewis acid catalyst, substrate, and product under synthetically relevant conditions. Overall, these rigorous mechanistic studies catalogue the factors critical to concise reaction design, and more specifically, detail the mechanistic features of carbonyl-olefin metathesis.




James Devery (Loyola University Chicago)