Graduation Term

Summer 2025

Degree Name

Master of Science (MS)

Department

Department of Chemistry

Committee Chair

Andy Mitchell

Committee Member

Shawn Hitchcock

Committee Member

Jeremy Driskell

Abstract

Cycloadditions can produce multiple bonds in a single step with excellent atom economy, and they are well suited to generate a great deal of complexity in one step. Cycloadditions proceed in a concerted mechanism, exemplified by renowned Diel-Alder (4+2). Unlike the well-known (4+2) cycloadditions, the studies into (5+2) cycloadditions are limited despite 7-membered ring systems being highly represented in biologically important natural products. The Mitchell group research has revolved around uncovering the mechanisms involved in silyloxypyrone (5+2) cycloadditions. Depending on the nature of the tethers attached to the oxidopyrylium, these reactions can deviate from a concerted pathway and instead proceed through stepwise mechanisms. Intriguingly, our investigation utilizing a di-carbonyl amide tether on the oxidopyrylium system unexpectedly yielded a rearrangement product rather than the anticipated cycloaddition adduct. We propose a mechanistic pathway for this transformation, encompassing a conjugate addition, a retro-electrocyclization, and a subsequent intramolecular aldol reaction. We have optimized the conditions for this novel rearrangement reaction and are currently exploring the scope and limitations

Access Type

Thesis-Open Access

DOI

https://doi.org/10.30707/ETD.1763755359.058656

Download

Available for download on Monday, September 10, 2029

Share

COinS