Analogues of acetyl acetonate as nucleophiles & ligands
thesisposted on 07.01.2014, 15:43 by Christopher J. Martin
This thesis contains the synthesis of a series of novelligands that include the enantiomerically pure 2-oxazoline moiety. The thesis also considers the application of new nucleophiles for the palladium catalysed allylic substitution reaction. The synthesis of enantiomerically enriched analogues of y-amino butyric acid (GABA) is presented. The first series of ligands are designed as analogues of acetyl acetonate (acac). The ligands include the enantiomerically pure 2-oxazoline ring and a carbonyl moiety. The ligands are available in good yield in two steps. The second series of ligands include a ligating sulfur atom. The synthesis of novel oxazoline-sulfide ligands is detailed. The diastereoselective oxidation of these ligands is considered. Diastereomerically pure oxazoline-sulfoxide ligands are prepared in good yield. New nucleophiles are applied to the palladium catalysed allylic substitution reaction. The substitution products are available in good yield and with excellent stereoselectivity. The synthesis of analogues of GABA is considered. The preparation of enantiomerically enriched a-substituted-y-amino butyric acids is presented. The stereocentre is introduced in the first step of the synthesis. The analogues are subsequently isolated in good yield after six steps.