Date of Award

Spring 5-2021

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

School

Mathematics and Natural Sciences

Committee Chair

Matthew G. Donahue

Committee Chair School

Mathematics and Natural Sciences

Committee Member 2

Julie A. Pigza

Committee Member 2 School

Mathematics and Natural Sciences

Committee Member 3

William Jarrett

Committee Member 3 School

Polymer Science and Engineering

Committee Member 4

Karl J. Wallace

Committee Member 4 School

Mathematics and Natural Sciences

Committee Member 5

Jacques K. Kessl

Committee Member 5 School

Mathematics and Natural Sciences

Abstract

This three-part dissertation is connected by the thread of utilizing sulfur-based functional groups, hence the power of sulfur. The first project was the development of a pentafluorobenzene based isothiocyanate chiral derivatizing agent (CDA), a class of compounds that differentiate enantiomers through covalent bond formation. This project, which was addressed using a combination of synthetic and computational methods and NMR analysis, gave rise to an CDA that was highly selective for amines and computationally predictable. Branching off of that, the second project demonstrated the use of two thioamide chiral solvating agents (CSAs), which had never been reported as a core functional group despite having favorable hydrogen bonding properties. By utilizing a series of NMR titrations of the analytes, either amide or mandelic acid, with the CSA. Both thioamide chiral solvating agents produced greater resolution than the well-known Kagan’s amide CSA, increasing the resolution of the enantiomeric pairs by 1H NMR up to 5x. CSAs without the hydrogen bonding capabilities or π acidic/basic pairing demonstrated poorer resolution. As a completely separate project, the use of computation to predict the crystal structures of sulfonamides, a well-known functional group was also started and so far, has shown that there is the potential for this to be viable for predicting the geometries of theoretically synthesizable sulfonamides, judging by the overall small errors observed for the dihedral angles, angles, and interatom distances observed between the crystal and computed structures for the sulfonamide core. Overall, these three projects display that, though much is known about these three sulfur-based functional groups, there is still much to learn about them and the manners in which they can be utilized.

ORCID ID

0000-0003-3839-7579

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