Gold(I) catalyst supported by poly(methylene phosphine)-co-styrene in the hydroamination of alkynes with arylamines
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Woods, Nolton Takashi
issued: 2023-09-15T00:05:14Z
issued: 2023
related degree: Master of Science - MSc
degree grantor: University of British Columbia
description: This thesis outlines the use of a phosphorus containing copolymer as a ligand for gold-catalyzed hydroaminations. Specifically, the phosphine moieties within the backbone of a random copolymer of styrene (S) and methylenephosphine (MP), PMP-co-PS function as P-ligands for gold(I) to afford a pre-catalyst. In Chapter 2, the use of the phosphorus-containing copolymer PMP-co-PS as a ligand for gold(I) is described. The activity of the acquired pre-catalyst PMP(AuCl)-co-PS in the intermolecular hydroamination of alkynes with arylamines (H₂NAr, Ar=Ph,4-NO₂Ph,etc.) is compared with the activity of model pre-catalysts (i.e., Ph₃PAuCl and MesP(AuCl)CHPh₂). Abstraction of the chloride from gold(I) using AgOTf was required for each pre-catalyst to obtain the active catalyst. In hydroaminations of phenylacetylene with arylamines employing pre-catalyst PMP(AuCl)-co-PS and following the above activation process selectively affords the Markovnikov products in good yields. In hydroaminations of diphenylacetylene with arylamines as substrates, the polymer-supported pre-catalyst was not as active; however, moderate yields of the imine and enamine product(s) were formed. Importantly, the polymer support allowed for the isolation of the catalyst from the products. The recovered catalyst could be recycled in additional cycles without the addition of fresh catalyst or AgOTf. It was determined that reducing the amount of gold(I) present to phosphorus in the polymer-supported pre-catalyst resulted in the improved stability of the active catalyst with sustained yields in the recycling reactions. In conclusion, PMP-co-PS was shown to be an effective support in gold catalysis that could be recovered and recycled for further use.
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/85921
note: Gold(I) Catalyst Supported by Poly(methylene phosphine)-co-Styrene in the Hydroamination of Alkynes with Arylamines by Nolton Takashi Woods B.Sc., Middle Tennessee State University, 2019 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) August 2023 © Nolton Takashi Woods, 2023 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the thesis entitled: Gold(I) Catalyst Supported by Poly(methylene phosphine)-co-Styrene in the Hydroamination of Alkyne with Arylamines submitted by Nolton Takashi Woods in partial fulfilment of the requirements for the degree of Master of Science in Chemistry Examining Committee: Dr. Derek P. Gates, Professor, Department of Chemistry, UBC Supervisor Dr. Laurel L. Schafer, Professor, Department of Chemistry, UBC Supervisory Committee Member Dr. Gregory R. Dake, Professor, Department of Chemistry, UBC Supervisory Committee Member Dr. Parisa Mehrkhodavandi, Professor, Department of Chemistry, UBC Additional Examiner iii Abstract This thesis outlines the use of a phosphorus containing copolymer as a ligand for gold-catalyzed hydroaminations. Specifically, the phosphine moieties within the backbone of a random copolymer of styrene (S) and methylenephosphine (MP), PMP-co-PS function as P-ligands for gold(I) to afford a pre-catalyst. In Chapter 2, the use of the phosphorus-containing copolymer PMP-co-PS as a ligand for gold(I) is described. The activity of the acquired pre-catalyst PMP(AuCl)-co-PS in the intermolecular hydroamination of alkynes with arylamines (H2NAr, Ar=Ph,4-NO2Ph,etc.) is compared with the activity of model pre-catalysts (i.e., Ph3PAuCl and MesP(AuCl)CHPh2). Abstraction of the chloride from gold(I) using AgOTf was required for each pre-catalyst to obtain the active catalyst. In hydroamin…
has type: Thesis/Dissertation
date issued: 2023-11
is shown at: 10.14288/1.0435878
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: Gates, Derek P.
type: Text
identifier URI: http://hdl.handle.net/2429/85921