Title: Regio- and Stereocontrol with Anions and Radicals
Dienolates and their synthetic equivalents provide a versatile platform for regioselective functionalization protocols owing to their ambident reactivity. Exploration of radical additions to these synthons is examined as a potential solution to the problem of γ-functionalization of cyclic ketones. In addition, anioinic dienolates are studied as unusual regiodivergent branch points for the synthesis of halogenated arenes from common, readily available precursors. Aspects of regio- and stereoselectivity are important components that provide mechanistic insights into these transformations. In separate studies, selective scission of carbon–carbon bonds is investigated using ring strain as a directing element and activating effect. Applications of these strategies in target-directed synthesis efforts are underway.