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Kinetic Resolution of Cyclic Enol Ethers by Pd-Catalyzed [1,3] O-C Rearrangement

Zirimwabagabo, Jean-Olivier (2014) Kinetic Resolution of Cyclic Enol Ethers by Pd-Catalyzed [1,3] O-C Rearrangement. PhD thesis, University of Sheffield.

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Pd-rearrangement thesis final.docx
Restricted until 1 May 2024.

Abstract

Abstract This thesis concerns the development of kinetic resolution of cyclic enol ethers utilizing a Pd-catalyzed [1,3] O-C rearrangement reaction. The required enol ethers were prepared from commercially available starting materials in good to excellent yields. The Pd-catalyzed [1,3] O-C rearrangement of these enol ethers in the presence of a chiral ligand proceeds smoothly via a kinetic resolution process returning remaining starting material with low to excellent levels of enantioselectivity. Enantiomerically enriched enol ethers were further transformed to a series of carbo- and heterocyclic products in good yield and with excellent levels of stereocontrol. Synthesis of (R)-goniothalamin was successfully accomplished via stereoselective transformations from an enantioenriched enol ether starting material. Aspects of the reaction mechanism are described, which resulted in the development of a model that explains the observed selectivities in the kinetic resolution. DFT studies aimed at providing a better understanding of the underpinning reasons for these selectivities are also described.

Item Type: Thesis (PhD)
Academic Units: The University of Sheffield > Faculty of Science (Sheffield) > Chemistry (Sheffield)
Depositing User: Dr Jean-Olivier Zirimwabagabo
Date Deposited: 25 Mar 2015 13:39
Last Modified: 25 Mar 2015 13:39
URI: http://etheses.whiterose.ac.uk/id/eprint/7105

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