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Title: Towards the synthesis of α-diazo-β-ketosulfoximines
Author: Goretta, Sarah Anaïs Emilie
Awarding Body: (UCL) University College London
Current Institution: University College London (University of London)
Date of Award: 2007
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This thesis presents the work and the methodology undertaken towards the synthesis of ot-diazosulfoximines as chiral analogues of cc-diazosulfones, as well as the work achieved to investigate novel chemistry for ot-diazosulfones. Towards acyclic a-diazo-p-ketosulfoximines Sulfoximines proved to have unexpected behaviour during the course of this work in two key-steps. In order to overcome these difficulties, different substrates were targeted and thus, various methods to synthesise acyclic N-alkyl, N-aryl or N-acyl sulfoximines are presented here. Several methods to generate diazo compounds are described, diazo transfer reaction and the use of N-nitroso carbamate attempts to obtain sulfoximine-substituted carbenes through the use of hypervalent iodine(III) were also investigated. Towards cyclic a-diazo-p-ketosulfoximines 6-Membered ring sulfoximines were targeted and starting from the corresponding sulfoxides, various sulfoximination methods were investigated, as well as their compatibility with other functional groups. A particular attention was given to the relative stereochemistry of substituents and its influence on the behaviour of the substrates during the reactions. Novel diazosulfones Previous studies have shown that C-silylation of diazoesters expands the scope of chemistry which can be carried out we therefore aimed to discover if the C-silylation of diazosulfones led a similar modification of reactivity. In parallel, we also tried to develop a hybrid of Gilbert-Seyferth reagent, diethyl (diazomethyl)phosphonate, and Julia-Kocienski olefination reagent, l-phenyl-l/ftetrazol-5-yl sulfone, which we expected to behave in a similar way but which could have enhanced reactivity, stability, and ease of use.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available