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Synthesis of chiral lactones via the baeyer villiger oxidation of cyclic aromatic acetoxy ketones novel annulation reactions of 2-propynyl-1,3-dicarbonyl compounds to form pyrroles addition of acyl phosphonates to diethyl cyanophosphonate (depc)

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2009
Aybey, Asuman
Chiral Baeyer-Villiger (BV) oxidation of cyclic ketones allows rapid access to asymmetric lactones as valuable intermediates in organic chemistry and frequently encountered precursors in enantioselective synthesis. In the first part, BV oxidation of functionalized ketones, especially cyclic -hydroxy and acetoxy ketones is described which could be a straightforward route to the -hydroxy lactones and -hydroxyalkanoic acid derivatives. The -acetoxylation of indanone, tetralone and chromanone derivatives by using Mn(OAc)3 followed by the enzyme catalyzed kinetic resolution of acetoxy ketones gives both of the enantiomers of -acetoxy ketones in good chemical and optical yields. The Bayer-Villiger oxidation of -acetoxy ketones with m-CPBA, CF3SO3H, and CH2Cl2, at rt gives the corresponding lactones without racemization. The phenyl moiety migrates selectively in order to form lactones. The mild hydrolysis of lactones affords phenolic -hydroxycarboxylic acid derivatives. Because of the high importance of pyrrole derivatives which exist in the structure of many natural products possessing biological activity beside their valuable feature of being versatile building blocks in organic synthesis and important starting materials for various synthetic transformations, a convenient method for the synthesis of 1,2,3,5-tetrasubstituted pyrrole derivatives starting from 1,3,-dicarbonyl compounds throuh acid catalyzed cyclization reaction is presented in the second part of the thesis. Alkylation of 1,3-dicarbonyl compound with propargyl bromide followed by one step cyclization with the introduction of primary amines in the presence of catalytic amount of trifluoroacetic acid (TFA) affords the corresponding pyrrole derivatives in high yields. The third part of the thesis describes the cyano-phosphorylation of various alkyl and aryl phosphonates in the presence of diethyl cyanophosphonate (DEPC) as the phosphorylating agent under the promotion of the KCN catalyst. Reaction of acyl phosphonates with DEPC forms the phosphonocyanohydrin-O-phosphates which are the important starting materials of quaternary α-hydroxy carboxylic acid and phosphonate containing β-aminoalcohol derivatives.