Sponsor
Portland State University. Department of Chemistry
First Advisor
David R. Stuart
Term of Graduation
Spring 2025
Date of Publication
6-4-2025
Document Type
Dissertation
Degree Name
Doctor of Philosophy (Ph.D.) in Chemistry
Department
Chemistry
Language
English
Subjects
Iodonium, Kinetic, Thermodynamic
DOI
10.15760/etd.3971
Physical Description
1 online resource (xii, 334 pages)
Abstract
Benzenoid rings are fundamental structural motifs in organic chemistry, widely recognized for their prevalence in natural products, pharmaceuticals, agrochemicals, and functional materials. Transition metal-catalyzed arylation, using catalysts such as palladium, nickel, or copper, has revolutionized C-C, C-O, and C-N bond formation, offering broad substrate scope and high efficiency. Among the reagents developed for efficient aryl group transfer, diaryliodonium salts have emerged as particularly powerful tools. Diaryliodonium salts facilitate metal-free arylations across a broad spectrum of nucleophiles, offering high reactivity, operational simplicity and environmental compatibility. The versatility of diaryliodonium salts has led to their widespread adoption as efficient arylating reagent in pharmaceutical and agrochemical. Despite significant advances in the application of diaryliodonium salts, critical knowledge gaps persist regarding their fundamental solution phase behavior and mechanistic reactivity. To address this knowledge gap, this work focuses on investigating the solution phase dynamics of diaryliodonium salts and provides mechanistic insights of their role in N- and O- arylation reactions.
The initial study focused on determining the Lewis basicity parameters of synthetically relevant amines which are used in several arylation reactions with diaryliodonium salts. This study also demonstrated distinct solvent effects in the interaction of anionic and neutral Lewis bases. The observed solvent effects further highlighted the need for a deeper investigation into the speciation of diaryliodonium salts in solution. The extent of ion pairing was quantified by determining the association constant of iodonium salts with different combinations of counter anion and solvent. The Lewis acidity parameter was redefined by including the extent of ion pairing of iodonium salts in solution. Next, the impact of counter in N-arylation reactions with diaryliodonium salts were described. Finally, kinetic studies were conducted to understand the O-arylation pathway of phenols with diaryliodonium salts. This study provided significant insights into the probable different pathways that O- arylation reactions can undergo with diaryliodonium salts. The overall aim of the study was to develop a more complete understanding of the reactivity of diaryliodonium salts in solution by thermodynamic and kinetic studies.
Rights
© 2025 Soocheta Jha
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Persistent Identifier
https://archives.pdx.edu/ds/psu/43913
Recommended Citation
Jha, Soocheta, "Investigation into Thermodynamic and Kinetic Phenomena in Arylation Reactions with Diaryliodonium Salts" (2025). Dissertations and Theses. Paper 6880.
https://doi.org/10.15760/etd.3971