Portland State University. Department of Chemistry
David R. Stuart
Term of Graduation
Date of Publication
Doctor of Philosophy (Ph.D.) in Chemistry
Arylation, Organic compounds -- Synthesis
1 online resource (xi, 257 pages)
Substituted benzenoid rings are a prevalent motif in many industries including high tech, agrochemicals, and pharmaceuticals. As a result, the arylation of chemical compounds is a highly sought-after chemical transformation. There are many literature methods to achieve this chemical transformation, nucleophilic aromatic substitution and transition metal catalysis are both widely used and studied. Diaryliodonium salt mediated chemistry is an attractive alternative to these methods as it does not require the expensive toxic metals and designer ligands of transition metal catalysis and is not restricted to electron deficient aryl rings with specific substitution patterns like nucleophilic aromatic substitution.
Many diaryliodonium salt arylation reactions rely upon symmetric diaryliodonium salts that are difficult to synthesize and have poor atom economy and are undesirable for complex aryl groups. I have developed synthetic pathways to form diaryl and alkyl-aryl ether molecules that are high yielding and functional group tolerant using easy to manufacture unsymmetric aryl(TMP) iodonium tosylate salts. These reactions are operated at low temperatures under mild conditions and allow for many different functional groups, substitution patterns and electronic effects on the aryl group. Electron rich aryl groups are not prominent in the diaryliodonium salt literature especially in alkyl-aryl ether synthesis, the synthetic routes I developed show competitive yields with a variety of electron rich aryl groups, expanding the scope of this chemistry.
I have also developed an efficient high yielding methodology for counter anion metathesis of diaryliodonium salts using solid state columns of exchange salt made from common laboratory supplies. Literature reactions are highly inefficient and use vast excess of exchange salt; the chemistry I developed allows for the reuse of exchange salt for more economic and efficient counter anion metathesis.
© 2022 Rory Tennessee Gallagher
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Gallagher, Rory Tennessee, "Synthesis of Diaryl and Alkyl-Aryl Ethers via Diaryl Iodonium Reagents" (2022). Dissertations and Theses. Paper 5987.