Development and deployment of automated monitoring methodologies mowards investigations of heterogeneous and biphasic reactions
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Daponte, Jordan Ashton
issued: 2019-11-07T18:27:41Z
issued: 2019
related degree: Master of Science - MSc
degree grantor: University of British Columbia
description: Mechanistic insight is fundamental to understanding a reaction and essential towards accessing desired product(s) in high yield, enantiopurity, and efficiency. Key to unlocking these investigations are developing tools that can monitor as many reactive species, intermediates, and products over the course of a reaction as possible. In the case of heterogeneous and biphasic systems, this analysis requires the development of new monitoring methodologies that can probe the complex equilibria, solubilities, mass transfer events, and catalytic cycles associated with the reaction. Herein, the development and deployment of reaction monitoring methods for the study of heterogeneous and biphasic reactions is discussed. These methodologies were deployed in two case studies, the first of which involved investigation of stereoselectivities of a proline catalyzed aldol reaction, while the second probed a biphasic reaction for an enantioselective spirocyclization catalyzed by a doubly quaternized cinchona alkaloid. The monitoring platforms allowed for the identification of water as the primary source of stereoselectivity in the proline-catalyzed aldol reaction, while also identifying the observed rate law, catalyst deactivation, and gaining insight into product behaviours. Investigations suggest that stereoselectivity likely originates from differences in transition states arising from the presence of water, rather than through kinetic phenomena. In the case of biphasic systems, a combined approach utilizing phase selective and heterogeneous sampling allowed for tracking of reaction species across both phases, allowing for insight into the reaction rate law, catalyst degradation, mass transfer behaviour, and temperature dependence studies. These results suggest that productive spirocyclization is balanced against inescapable catalyst degradation, with future optimization likely requiring new catalyst designs to counteract this relationship. The deployment of these monitoring metho…
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/72222
note: Development and Deployment of Automated Monitoring Methodologies Towards Investigations of Heterogeneous and Biphasic Reactions by Jordan Ashton Daponte B.Sc., University of Toronto, 2017 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Chemistry) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) November 2019 © Jordan Ashton Daponte, 2019 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, a thesis/dissertation entitled: Development and Deployment of Automated Monitoring Methodologies Towards Investigations of Heterogeneous and Biphasic Reactions submitted by Jordan Daponte in partial fulfillment of the requirements for the degree of Master of Science in Chemistry Examining Committee: Dr. Jason E. Hein Supervisor Dr. Glenn Sammis Supervisory Committee Member Dr. Gregory Dake Supervisory Committee Member iii Abstract Mechanistic insight is fundamental to understanding a reaction and essential towards accessing desired product(s) in high yield, enantiopurity, and efficiency. Key to unlocking these investigations are developing tools that can monitor as many reactive species, intermediates, and products over the course of a reaction as possible. In the case of heterogeneous and biphasic systems, this analysis requires the development of new monitoring methodologies that can probe the complex equilibria, solubilities, mass transfer events, and catalytic cycles associated with the reaction. Herein, the development and deployment of reaction monitoring methods for the study of heterogeneous and biphasic reactions is discussed. These methodologies were deployed in two case studies, the first of which involved investigation of stereoselectivities of a proline catalyzed aldol reaction, while the second probed a biphasic reaction for an enantioselective spirocyclization catalyzed by a doubly…
has type: Thesis/Dissertation
date issued: 2020-05
is shown at: 10.14288/1.0385126
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
type: Text
identifier URI: http://hdl.handle.net/2429/72222