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Ttransition Metals-catalyzed Functionalization Of Ketones Derivatives

Posted on:2017-01-12Degree:MasterType:Thesis
Country:ChinaCandidate:T B ChenFull Text:PDF
GTID:2311330485977304Subject:Organic Chemistry
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C-H bond is one of the common functional-groups among organic compounds.C-H bond activation is one of the hot topics in the field of organic sythesis methodology. Mild and selsctive transformtion of this type will undoubtedl find widespread application across the chemistry. Transition metal-catalyzed C-H bond functionalization is one of the most efficient, convenient and economic methodologies for the systhsis of target compounds based on easily available starting materials with short synthetic routes, which conform to the requirement of modern green synthetic chemistry. This methodology opened a new route to form C-C and C-X bonds and attracted much attention of chemists.In chapter one, we summarized the achievements of transition metal-catalyzed C(sp3)-H bonds activation which consist of five parts, including the formation of C-Cl,C-Br, C-I, C-O, C=C bonds.In chapter two, we developed efficient methods for activation of ?-bromination of 2-methylacetophenones. Copper mediated bromination afforded 2-bromo-1-phenyethanone both in one step and with high chemo- and regioselectivities, where the acetyl group acted as a directing group.In chapter three, we have reported ?-oxidation of aromatic ketones. A variety of2-(2-methylphenyl)-2-oxo-ethyl acetates were successfully prepared in acetic acid,using palladium acetate as catalyst and(diacetoxyiodo)benzene as oxidant. The reaction tolerated a broad scope of functional groups. This reaction has a certain electronic effect and steric effect.In chapter four,(E)-1,4-Enediones were synthesized efficiently via sp3 C-H activation and coupling of aromatic methyl ketones, using palladium acetate as catalyst, copper bromide as oxidant in N, N-dimethylformide. The transformation has broad substrate scope.
Keywords/Search Tags:Methylacetophenones, C-H bond functionalization, Bromination, Acetoxylation, Coupling
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