Date of Award
Doctor of Philosophy
Richard C. Larock
George A. Kraus
Chapter 1. A large number of functionally-substituted 2-alkyn-1-one O-methyl oximes have been cyclized under mild reaction conditions in the presence of ICl to give the corresponding 4-iodoisoxazoles in moderate to excellent yields. The resulting 4-iodoisoxazoles undergo various palladium-catalyzed reactions to yield 3,4,5-trisubstituted isoxazoles, including valdecoxib.;Chapter 2. The iodocyclization of O-methyloximes of 2-alkyn-1-ones affords 4-iodoisoxazoles, which undergo various palladium-catalyzed reactions to yield 3,4,5-trisubstituted isoxazoles. The palladium-catalyzed processes have been adapted to parallel synthesis utilizing commercially available boronic acid, acetylene, styrene and amine sublibraries. Accordingly, a diverse 51-member library of 3,4,5-trisubstituted isoxazoles has been generated.;Chapter 3. A number of new functionally-substituted 1-acyl-5-hydroxy-4,5-dihydro-1H-pyrazoles have been prepared in moderate to excellent yields from the corresponding 2-alkyn-1-ones. The resulting dihydropyrazoles undergo dehydration and iodination in the presence of ICl and Li2CO3 at room temperature to provide 1-acyl-4-iodo-1H-pyrazoles.;Chapter 4. Oxazolium salts are readily prepared by the iodine-induced cyclization of alkynamides to form. The resulting oxazolium iodide salts are highly stable and attempts at their dequaternization have been met with limited success.;Chapter 5. Fluoren-9-ones and derivatives are readily prepared in good yields by the annulation of in situ generated arynes by 2-haloarenecarboxaldehydes in the presence of a palladium catalyst.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Jesse Page Waldo
Waldo, Jesse Page, "Iodine and palladium approaches to medicinally interesting heterocycles and carbocycles" (2008). Retrospective Theses and Dissertations. 15817.