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Asymmetric transfer hydrogenation using Ru(II) complexes of heterocyclic TsDPEN ligands
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Barrios Rivera, Jonathan (2021) Asymmetric transfer hydrogenation using Ru(II) complexes of heterocyclic TsDPEN ligands. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3755526~S15
Abstract
TsDPEN ligands containing a pyridine or a triazole group on the amine nitrogen atom work effectively in a tridentate catalyst system with Ru3(CO)12 in the asymmetric transfer hydrogenation of ketones. Derivatives of the pyridine ligand have been synthesised for further investigation of the catalyst system.
A range of TsDPEN ligands containing heteroaromatic groups on the amine nitrogen atom were also synthesised and evaluated as either bidentate or tridentate ligands in the asymmetric transfer hydrogenation of ketones. These bidentate and tridentate ligands demonstrate a mutual exclusivity directly related to their function as catalysts.
Substituted-acetophenones are reduced with the bidentate ligands using either a preformed catalyst or through an in situ catalyst. A series of ketones were reduced with the corresponding catalysts, formed from the bidentate and tridentate ligands, permitting the ready identification of an optimal catalyst for the ATH of each ketone.
TsDPEN ligands containing non-aromatic heterocyclic groups on the amine nitrogen atom were also synthesised and evaluated as either bidentate or tridentate ligands. Such ligands contain a third chiral centre leading to either active or inactive ligands in ATH.
The asymmetric transfer hydrogenation of 1-phenyl-3,4-dihydroisoquinolines with a furan-containing catalyst results in the formation of the corresponding product in high enantiomeric excess. A further application of the catalyst on to the reduction of 1-aryl-3,4-dihydroisoquinolines containing meta or para-substituted aromatic groups gave products in high enantiomeric excess. The approach solves a long-standing challenge in the asymmetric transfer hydrogenation of dihydroisoquinolines.
Derivatives of a furan-containing catalyst have been synthesised and compared in the ATH of acetophenone. A scale up of the preparation of a furan catalyst has been attempted. A variety of synthetic methods to support a furan catalyst on to a solid support have been designed and executed.
A range of α-heteroaromatic ketones were synthesised and asymmetrically reduced with the furan-containing catalyst. Alcohol products were obtained in high enantiomeric excess.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Ruthenium compounds, Hydrogenation, Heterocyclic compounds, Ligands | ||||
Official Date: | August 2021 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Wills, Martin | ||||
Sponsors: | GoldenKeys High-tech Materials Co., Ltd. ; University of Warwick | ||||
Extent: | iv, 291 leaves : illustrations, charts | ||||
Language: | eng |
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