Enyne metathesis methods applied toward the total synthesis of natural products
Clark, Daniel A.
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Enyne metathesis is an extremely powerful method for the synthesis of conjugated 1,3-dienes that possess a variety of substitution patterns. This atom-economical transformation allows for complex functionality to be brought together expediently in a catalytic environment. Our primary focus is to develop enyne metathesis methods catalyzed by the Grubbs family of ruthenium carbenes. The combination of enyne metathesis and another reaction in either a tandem or sequential manner greatly enhances the complexity-building potential of enyne metathesis. State of the art, in enyne metathesis only allows certain substitution patterns to be accessed. We are interested in expanding the substitution patterns that can be accessed by enyne metathesis in a stereodefined manner. Further, our group is interested in using tandem enyne metathesis reactions to create ring systems. The first part of this thesis will describe our studies to expand the enyne metathesis substitution patterns by tandem enyne metathesis and subsequent Ireland-Claisen rearrangement. The second part of this thesis will cover our efforts to develop a regioselective ring expansion methodology utilizing strained bicyclic systems to create bicycloheptadienes. Our mechanistic hypothesis as well as scope of reaction will be described. The third section will detail our efforts toward the synthesis of isodaucane terpene natural products utilizing our regioselective methylene-free ring expansion. Our dead ends and detours met along the way will be described.