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|Title: ||Investigations in Transition Metal Catalysis: Development of a Palladium Catalyzed Carboesterification of Olefins and Synthesis of Chiral Sulfoxide Pincer Ligands|
|Authors: ||Jardine, Katherine Jane|
|Advisor: ||Dong, Vy Maria|
|Keywords: ||Transition Metal Catalysis|
|Issue Date: ||6-Apr-2010|
|Abstract: ||The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed.
Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.|
|Appears in Collections:||Master|
Department of Chemistry - Master theses
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