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Title: The asymmetric synthesis and reactions of α-functionalised organometallic reagents
Author: Rayner, Peter
ISNI:       0000 0004 2744 7275
Awarding Body: University of York
Current Institution: University of York
Date of Award: 2013
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This thesis describes the development of new methods for the asymmetric synthesis of α-alkoxy and α-amino organometallic reagents. Two approaches were taken: (i) sulfoxide → magnesium exchange; (ii) asymmetric lithiation-trapping using chiral bases. A review of this area is provided in Chapter One. Chapter Two details the synthesis of α-alkoxy sulfoxides A in 99:1 er by asymmetric lithiation using s-BuLi and chiral diamines and trapping with Andersen’s sulfinate. In addition, an investigation into the lack of stereospecificity at sulfur during the trapping process is presented. Finally, a sulfoxide → magnesium exchange was used to convert the α-alkoxy sulfoxides into α-alkoxy Grignard reagents B and subsequent trapping allows access to a range of products as single enantiomers. The remarkable configurational stability of α-alkoxy Grignard reagents when compared to their organolithium counterparts is of particular note. Attempts to use a similar method to synthesise α-amino sulfoxides in 99:1 er is described in Chapter Three. Furthermore, insights are given into the surprising instability of unsubstituted α-amino sulfoxides. Novel α-amino sulfoxides C were designed to prohibit sulfoxide elimination. From the isolatable α-amino sulfoxides, the synthesis and reactions of α-amino Grignard reagents D in 99:1 er via sulfoxide → magnesium exchange is reported. In Chapter Four, an investigation into the mechanism of the asymmetric lithiation trapping of N-thiopivaloyl azetidine E using s-BuLi and chiral diamines is presented. The configurational stability of the organolithium intermediate F was determined at −78°C and the scope of electrophilic trapping was investigated.
Supervisor: O'Brien, Peter Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available