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The Synthesis of Rhodium Catalyst-Organic Frameworks for Isomerization and Continuous-Flow Hydrogenation Reactions Open Access

Descriptions

Other title
Subject/Keyword
Catalysis
BINAP
Heterogeneous
Hydrogenation
Isomerization
Rhodium
Continuous-Flow
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Corkum, Elizabeth G
Supervisor and department
Bergens, Steven (Chemistry)
Examining committee member and department
Crudden, Cathleen (Chemistry)
West, Frederick (Chemistry)
Lundgren, Rylan (Chemistry)
de Klerk, Arno (Chemical and Materials Engineering)
Department
Department of Chemistry
Specialization

Date accepted
2013-07-31T10:37:02Z
Graduation date
2013-11
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
The development of immobilized asymmetric catalysts is of vital importance as it would allow for easy catalyst recovery from the reaction mixture and reuse. One strategy for immobilization involves the synthesis of insoluble polymer-supported catalysts. Most polymeric catalysts are made by polymerizing a chiral ligand, or grafting the ligand to a polymer support, followed by metallation of the ligand sites. The resulting catalysts are often plagued by poor activity and reusability due to incomplete metallation, limited access to catalytic active sites and metal leaching. The Bergens group developed a method where a ruthenium metal-containing monomer (MCM) is directly polymerized by alternating ring-opening metathesis polymerization (altROMP) and deposited on insoluble barium salts. The resulting catalyst-organic frameworks (COFs) exhibited remarkable reuse with no drop in activity or selectivity and no detectable ruthenium leaching. This dissertation describes the extension of the altROMP methodology to rhodium-BINAP containing catalysts and their use in the intramolecular cycloisomerization of 1,6-enynes, solvent-free allylic alcohol isomerizations and continuous-flow olefin hydrogenations. The altROMP of MCMs [RhCl((R)-5,5ʹ-dinorimido-BINAP)]2 (I) and [Rh(NBD)((R)-5,5ʹ-dinorimido-BINAP)](SbF6) (II), with cyclooctene as a spacer monomer, and with RuCl2(CHPh)(PCy3)2 as the ROMP catalyst, gave two novel rhodium-BINAP COFs, Ia and IIa respectively, that were subsequently deposited on BaSO4 or Ba-L-tartrate. Framework Ia sustained up to six reuses and provided the highest TONs to date (up to 890), with no drop in enantioselectivity (95-99.9% ee), in the cycloisomerization of 1,6-enynes. As well, a key intermediate in the production of pharmaceutical (+)-pilocarpine was afforded in >99.9% ee. Framework Ia also provided the highest TONs to date (up to 38,000) for the rhodium catalyzed isomerization of secondary allylic alcohols with catalyst loadings as low as 0.0025 mol%. In both cases, the COF proved to be more active and selective than the parent homogeneous catalyst. Framework IIa proved to be highly active in the continuous-flow hydrogenation of a variety of olefin-containing substrates and sustained up to 55,700 TOs over a period of 30 days in the H-Cube® continuous-flow reactor. As well, in a preliminary study, >99.9% ee was obtained in the continuous-flow hydrogenation of itaconic acid by framework Ia.
Language
English
DOI
doi:10.7939/R3GF0N47Q
Rights
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
Citation for previous publication
Corkum, E. G.; Hass, M. J.; Sullivan, A. D.; Bergens, S. H. Organic Letters 2011, 13, 3522.Corkum, E. G.; Kalapugama, S.; Hass, M. J.; Bergens, S. H. RSC Advances 2012, 2, 3473.

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