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The method of asymmetric oxidation of ketones may become an important tool in obtaining bioactive hydroxylated carbonyl compounds. Scope and limitations and the mechanistic aspects of the method is not yet clear. The aim of the present project is to elucidate the possibilities of the direct oxidation of ketones and the use of the method in the synthesis of essential chiral compounds (sugar carba-analogues, chirons for bioactive compounds etc.); search for new methods for enantioselective transformation of carbonyl compounds. Prochiral, racemic and meso-ketones, diones and anhydrides will be used as the substrates. Research will be performed in the following directions: Asymmetric oxidation and search for new substrates- oxidation of functionalized cyclopentanediones cyclopentenones and hydroxycyclopentanones will be investigated. Synthesis of biologically interesting enantiomeric hydroxycarbonyl compounds- asymmetric oxidation of hydroxyenones and hydroxyketones etc. in order to get a-hydroxylated compounds. Sugar carba-analogues- possibilities of synthesis of sugar carba-analogues using the direct oxidation of ketones will be investigated. Synthesis of new antiviral (incl. anti-HIV) compounds will be considered. Enantiomeric lactones, carboxylic acids and sugar alkyl analogues- elucidation of the possibilities of synthesis of hydroxy carboxylic acids by asymmetric oxidation of 1,2-cyclopentanediones; synthesis of bioactive (anti-viral, anti-cancer) compounds and their analogues. Desymmetrisation of meso-anhydrides- new method for desymmetrisation of meso-anhydrides by using Sharpless catalyst. Secosterol D-ring- asymmetric oxidation of functionalised cyclobutanones. Mechanism of the asymmetric oxidation- the "favoured" and "unfavoured" conformations of Ti/substrate complex will be calculated in order to understand the enantioselectivity factors of the oxidation. |