Date of Award
Doctor of Philosophy (PhD)
Daniel C Whitehead, Committee Chair
Brian N Dominy
This thesis discloses two distinct applications of synthesized iodoarene-containing compounds: as hypervalent iodine (HI) organocatalysts and as biodegradable X-ray contrasting agents. This thesis also details a short chapter regarding the synthesis of rarely accessible chemical moieties: diazacyclobutenes and 2-imidothioimidates.
Recently, organohypervalent iodine compounds have prevailed as valuable synthetic reagents. These reagents have the ability to efficiently perform transition metal-like transformations while possessing environmentally friendly properties. However, a persistent obstacle in utilizing hypervalent iodine (HI) reagents has been promoting synthetic reactions with high reactivities and enantioselectivities. To this fact, it is necessary to further improve upon the field of hypervalent iodine chemistry, especially in the context of the development of new, modular, and tunable catalyst scaffolds.
The first chapter of this thesis reviews the background and history of hypervalent iodine compounds. The second chapter describes the progress that has been made in the field of catalysis, with emphasis on asymmetric organocatalysis. The third chapter details the advances that were made to design, develop, and understand the reactivity of iodoarene-containing catalysts in hypervalent iodine(III)-mediated transformations. Furthermore, the third chapter provides insight on merging the fields of hypervalent iodine chemistry with organocatalysis and asymmetric synthesis to generate chiral catalysts that can be used in valuable organic transformations. These organocatalysts have the potential to be broadly applicable and to impact synthetically useful transformations by imparting high yields and stereoselectivities.
Synthetic materials have proven to have a key role in the medical field. In particular, polymeric materials have exhibited significance as contrast imaging agents due to their inherent biodegradable and biocompatible profile. The fourth chapter of this thesis describes the efficient synthesis, characterization, and X-ray evaluation of several iodoarene-containing polyesters.
Synthetic chemists are continuously searching for novel and efficient bond-forming methods to produce new chemical species. The final chapter of this thesis describes a new strategy to generate unique chemical motifs (diazacyclobutenes and 2-imidothioimidates) via a formal [2+2] cycloaddition between electron rich alkynes and azodicarbonyl reagents.
Lex, Timothy R., "Developing Iodoarene Derivatives for Useful Oxidative Transformations and Biodegradable X-ray Materials" (2019). All Dissertations. 2460.