Sulfur in asymmetric synthesis
thesisposted on 04.07.2018, 13:36 by Serge Reignier
This thesis is divided into three chapters. The first chapter is a review of the literature methods utilised to date in the synthesis of non-racemic chiral sulfoxides, including resolution, stereospecific nucleophilic substitution at sulfur, asymmetric oxidation and enzymatic methods Also, this first chapter introduces briefly the palladium-catalysed allylic nucleophilic substitution reaction. It covers the nature of different factors which can influence on the enantiomeric excess. The second section deals with our approaches to the synthesis of potentially chelating sulfoxides of high enantiomeric purity and their subsequent application, mainly in the process of palladium-catalysed allylic nucleophilic substitution reactions as chiral ligands, but also their application as chiral auxiliaries in the synthesis of chiral α-hydroxy or α-amino ketones. This second chapter also deals with the design of a new class of chiral ammo-sulfides as ligand in the palladium-catalysed allylic nucleophilic substitution reaction. The most successful ligand synthesised enantiomerically pure N-(1,1-dimethylethyl)-N-(1S,2S)-2-[(1,1-dimethylethyl)thio]-1-methyl-2-phenylethyl-N-methylamine was applied successfully to the palladium-catalysed allylic nucleophilic substitution reaction, furnishing the product in up to 89% ee. The third part of this thesis deals with the experimental procedures undertaken in this work.