Expansion of the Anionic Amino-Cope Cascade and Deuteration of Monomers for the Creation of Perdeuterated Polymers

Abstract

In this dissertation, multiple methods for manipulating and harnessing the power of an anionicvariation of a known [3,3] rearrangement are presented, alongside efforts towards creating proton-free monomers for use in polymerization reactions with elemental sulfur to form hybrid organic polymers with novel IR transparency. Chapter 1 acts as an introduction to the modified [3,3] Cope cascade, and research is presented that introduced multiple new stereocenters into the products formed from the reaction. This work built upon the foundation laid by previous members in Jón Njarðarson’s research group, and thoroughly explored the reaction mechanism and transition states needed to form each product. Chapter 2 highlights the pursuit of an unexpected result while attempting to install a new quaternary center in the Cope rearrangement- an aromatic ring was formed from scratch via acyclic building blocks. The mechanism is pursued, and stereochemical analysis of key intermediates sheds light upon the stereochemistry needed for the reaction to proceed. Chapter 3 presents the results from a collaborative research project at the University of Arizona combining organic synthesis and optics - a fully deuterated, proton-free monomer is synthesized for use in polymerization reactions to create novel organic polymers for use in lenses with novel properties. This chapter highlights the intense difficulties of working with deuterium and presents the results of the first full “total synthesis” of such a monomer. Chapter 4 provides an analysis of FDA approved veterinary drugs, and their roles in human medicine. This analysis identifies the ways that these drugs are similar and different in human and animal systems, and provides a thorough analysis of these often under-represented drugs. Chapter 5 provides an analysis of the trends seen in FDA approved combination drugs, or drugs with more than one active ingredient. This first of its kind analysis consolidates data for these drugs in an easily digestible manner and provides a thorough reference for anybody wishing to learn more about the subject.