Use this URL to cite or link to this record in EThOS:
Title: Metal-catalysed desymmetrizations of meso-compounds
Author: Jacques, Reece
ISNI:       0000 0004 8507 7751
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2020
Availability of Full Text:
Access from EThOS:
Full text unavailable from EThOS. Please try the link below.
Access from Institution:
The work contained in this thesis describes transition metal-catalysed desymmetrizations of a diverse range of meso-bisphosphates to afford enantiopure compounds with multiple contiguous stereocenters. The projects focus on the resolution of pro-quaternary centers in the meso-substrates, as these desymmetrizations are underrepresented in organic synthesis. The first part of the thesis demonstrates the copper-catalysed asymmetric allylic alkylation of cyclic and acyclic meso-bisphosphates using alkylzirconium nucleophiles. The reaction was applied to increasingly complex starting materials, allowing access to products with up to 3 contiguous stereocenters and all-carbon quaternary centers with high enantioselectivity. Unsymmetrical bisphosphates were investigated to allow insight on the reaction mechanism and also underwent kinetic resolution successfully. In the second part, rhodium-catalysed asymmetric allylic arylation was applied to mesobisphosphates using boronic acid nucleophiles, which expanded on previous asymmetric sp2- sp3 couplings developed in the Fletcher group. Although the reaction was limited in substrate scope, high enantioselectivity was obtained. In addition, cyclic thiophosphates were investigated as electrophiles in a range of catalytic transformations.
Supervisor: Not available Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available