Date of Award
2025
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Matthias Brewer
Abstract
A primary focus of the Brewer research group is leveraging little-studied reactive intermediates for novel synthetic methodologies. In recent years, the Group has studied reactive intermediates generated from α-diazo-β-hydroxy carbonyls. For example, vinyl diazonium ions are a little-studied intermediate that can be generated by treating α-diazo-β-hydroxy carbonyls with mild acids. These species are potent electrophiles that react with even weak nucleophiles in conjugate addition reactions that retain the diazo functional group. The diazo functional group is one of the most versatile functional groups in organic chemistry, but they are very sensitive to many reaction conditions and do not survive many transformations, which is a unique feature of this reaction. This dissertation includes our investigations into the stereoelectronic factors that govern the diastereoselectivty of the conjugate addition of silyl enol ethers to vinyl diazonium ions to form 2-diazo1,5-dicarbonyls. The use of these products as precursors to stereochemically rich tetrahydrofuran rings via carbonyl ylide cycloaddition and intramolecular O-H insertion was also investigated. My discovery and development of the Lewis acid-catalyzed addition reaction of oxygen nucleophiles to vinyl diazonium ions to form α-diazo-β-alkoxy carbonyls and the intramolecular 1,3-dipolar cycloaddition reactions of these products is discussed. Finally, my evaluation of chiral catalysts for the asymmetric conjugate addition of indole to vinyl diazonium ions to prepare enantioenriched diazo-containing scaffolds that feature the biologically privileged indole moiety is described.
Language
en
Number of Pages
328 p.
Recommended Citation
Peck, Avery, "Conjugate Addition Reactions Of Vinyl Diazonium Ions Derived From Α-Diazo-Β-Hydroxy Carbonyls" (2025). Graduate College Dissertations and Theses. 2005.
https://scholarworks.uvm.edu/graddis/2005