Investigation of Conjugate Addition Initiated Cyclization Reactions of Dienyl Diketones and Progress Toward a Scalable Synthetic Route to (-) -Rocaglamide

In the first chapter, the bifurcated reactivity demonstrated by dienyl diketones is investigated. It was found that with secondary amines, the reaction proceeds through a 4 pi electrocyclization (Nazarov) mechanism takes place, leading to cyclopentenone products. However, if the tertiary amine DABCO is used, the reaction goes through a 6 pi electrocyclization, leading to 2H-pyran products. It was determined that both cyclization pathways are reversible, and an interesting retro-Nazarov reaction was realized. The factors controlling which product is formed are discussed. Interestingly, it was found that the Nazarov reaction could be promoted without the use of Lewis acid.;In the second chapter, the investigations into the development of a scalable, enantioselective synthetic strategy toward (-)-rocaglamide are discussed. Several different approaches have been investigated and the results are discussed. The most promising of which features a palladium catalyzed carbonylative annulation of an aryl alkyne. Current work is focusing on overcoming problems associated with the reactivity of this reaction. Future work includes potential synthetic derivatives to be synthesized for biological testing.