Investigations of one-pot synthetic transformations mediated by sulfuryl fluoride and thionyl fluoride
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Bolduc, Trevor G.
issued: 2023-10-03T16:12:46Z
issued: 2023
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: The development of mild, selective, efficient, and economical chemical transformations is a foundation of modern synthetic organic chemistry. These chemical processes may be utilized in the syntheses of pharmaceutical compounds, facilitating improved approaches to complex targets. Novel reagents are often created and studied during the development of these more effective protocols. This dissertation explores several synthetic applications of sulfuryl fluoride and thionyl fluoride as reagents in useful chemical processes. Little is known about the synthetic applications of thionyl fluoride, and the work presented herein includes some of the first investigations of this chemical as a reagent in synthetic organic chemistry. Chapter 2 describes the sulfuryl fluoride-mediated transformation of thiols to the corresponding 1,1-dihydrofluoroalkyl sulfide. The primary themes of the work outlined in this chapter include investigations into the chemoselectivity of the title reaction for thiols over other nucleophilic moieties, as well as an expansion of the scope of 1,1-dihydrofluoroalcohols. In Chapter 3, the kinetics of the one-pot sulfuryl fluoride-mediated activation and nucleophilic acyl substitution of carboxylic acids are explored using quantitative 1H and 19F nuclear magnetic resonance spectroscopy. The addition of a tetrabutylammonium halide salt additive as much as doubles the rate of formation of the intermediate acyl fluoride, yet there is no effect on the rate of consumption of this intermediate by the nucleophilic coupling partner. Contributions made to the substrate scope are further outlined in this chapter. Chapter 4 details a comprehensive study of several new synthetic applications of thionyl fluoride in the context of carboxylic acid activation. One-pot, column-free nucleophilic acyl substitutions and one-pot, mild reductions are described in this work. Activated esters, amides, and alcohols are all accessible via the corresponding acyl fluoride intermediat…
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/86054
note: INVESTIGATIONS OF ONE-POT SYNTHETIC TRANSFORMATIONS MEDIATED BY SULFURYL FLUORIDE AND THIONYL FLUORIDE by Trevor G. Bolduc B.Sc. (Honours), University of Victoria, 2018 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Chemistry) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) September 2023 © Trevor G. Bolduc, 2023 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the dissertation entitled: Investigations of One-Pot Synthetic Transformations Mediated by Sulfuryl Fluoride and Thionyl Fluoride submitted by Trevor G. Bolduc in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry Examining Committee: Glenn M. Sammis, Professor, Chemistry, UBC Supervisor Laurel L. Schafer, Professor, Chemistry, UBC Supervisory Committee Member Gregory R. Dake, Associate Professor, Chemistry, UBC University Examiner Allan K. Bertram, Professor, Chemistry, UBC University Examiner Additional Supervisory Committee Members: Jason E. Hein, Associate Professor, Chemistry, UBC Supervisory Committee Member Parisa Mehrkhodavandi, Professor, Chemistry, UBC Supervisory Committee Member iii Abstract The development of mild, selective, efficient, and economical chemical transformations is a foundation of modern synthetic organic chemistry. These chemical processes may be utilized in the syntheses of pharmaceutical compounds, facilitating improved approaches to complex targets. Novel reagents are often created and studied during the development of these more effective protocols. This dissertation explores several synthetic applications of sulfuryl fluoride and thionyl fluoride as reagents in useful chemical processes. Little is known about the synthetic applications of thionyl fluoride, and the work presented herein includes some of the first investigations of this chemical …
has type: Thesis/Dissertation
date issued: 2023-11
is shown at: 10.14288/1.0436926
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: Attribution-NonCommercial-NoDerivatives 4.0 International
rights URI: http://creativecommons.org/licenses/by-nc-nd/4.0/
scholar level: Graduate
contributor: Sammis, Glenn
type: Text
identifier URI: http://hdl.handle.net/2429/86054