Use this URL to cite or link to this record in EThOS:
Title: Organozirconocene nucleophiles in Cu-catalysed asymmetric transformations : methodologies, applications to total synthesis and NMR mechanistic studies
Author: Rideau, Emeline
ISNI:       0000 0004 6497 8630
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2016
Availability of Full Text:
Access from EThOS:
Full text unavailable from EThOS. Restricted access.
Access from Institution:
The development of powerful and adaptable methods to form new C-C bond enantioselectively is highly desirable. Many methodologies emerged in recent years using a wide array of nucleophilic organometallics and catalytic metals1,2. In this work, a general introduction on the current development of Cu-catalysed asymmetric additions is primarily described (Chapter 1). We particularly focus on the applications of such methodologies, the study of their mechanisms and the transition from using common organometallics in favour of milder and functional group tolerant nucleophiles such as organozirconocenes. We then present the development of new methods for asymmetric conjugate addition towards its application to the synthesis of prostaglandins (Part I). For example, we describe the use of alkenylzirconocene nucleophiles (Chapter 2) and conjugate additions of alkylzirconocenes to 5-membered rings3 (Chapter 3). We then investigated the application of these methodologies towards the total synthesis of a prostaglandin analogue, Latanoprost (Xalatan®) (Chapter 4). Then we carried out mechanistic studies by NMR (Part II). The mechanism of asymmetric allylic alkylation of alkylzirconocene to allylchlorides4 (Chapter 5) and allylphosphates (Chapter 6) is discussed in detail. We also developed and investigated the heterocyclic asymmetric allylic alkylation of alkylzirconocene5 (Chapter 7). Finally we describe the NMR mechanistic studies of asymmetric conjugate addition of alkylzirconocenes (Chapter 8).
Supervisor: Fletcher, Stephen P. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available