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Title: Kinetic resolution of cyclic enol ethers by Pd-catalyzed [1,3] O-C rearrangement
Author: Zirimwabagabo, Jean-Olivier
ISNI:       0000 0004 5346 9208
Awarding Body: University of Sheffield
Current Institution: University of Sheffield
Date of Award: 2014
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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.
Supervisor: Harrity, Joe Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available