Investigation of Sulfur(VI) Chemistry

Mendonca Matos, Priscilla (2019) Investigation of Sulfur(VI) Chemistry. PhD thesis, University of Nottingham.

[img] PDF (Thesis - as examined) - Repository staff only until 17 July 2021. Subsequently available to Repository staff only - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader
Download (19MB)

Abstract

This thesis focuses closely on the latest advancements in the synthesis of sulfur(VI) analogues, namely sulfonimidates and sulfoximines. A detailed analysis of their applications and syntheses is reported into two sections: synthesis of racemic sulfoximines from acyclic sulfonimidates, and secondly, the synthesis of enantioenriched NH-sulfoximines from cyclic sulfonimidates.

The route towards the synthesis of racemic sulfoximine products starting from sulfinamides (sulfur(IV) species) that were converted into sulfonimidates through a hypervalent iodine mediated oxidative alkoxylation reaction and explored in detail to allow modification of the core structure. Subjecting the acyclic sulfonimidates to Grignard reaction conditions allowed a general method for C-S bond formation to be explored and adding a third point of diversity to the sulfoximine products.

The second part of the results and discussion closely follows the synthesis of cyclic sulfonimidates and their subsequent conversion into sulfoximine products. Oxidative chlorination of sulfinamides followed by cyclisation allows access to cyclic sulfonimidates. Structural diversity was investigated further through Grignard addition to these cyclic sulfonimidate templates. Furthermore, the stereochemical outcome of all steps towards sulfoximines was carefully monitored by X-ray crystallography. Pleasingly, NH-sulfoximines were isolated using basic conditions under an oxygen atmosphere to cleave the phenylethanol moiety with no loss of stereochemical information at sulfur during this transformation giving free NH-sulfoximines with excellent enantiomeric excess.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Stockman, Robert
Keywords: sulfoximines; sulfonimidates; organic compounds; synthesis
Subjects: Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 56986
Depositing User: Mendonca Matos, Priscilla
Date Deposited: 25 Oct 2019 12:21
Last Modified: 06 May 2020 13:34
URI: http://eprints.nottingham.ac.uk/id/eprint/56986

Actions (Archive Staff Only)

Edit View Edit View