dc.contributor.advisor | Tunge, Jon A | |
dc.contributor.author | Trivedi, Rushi | |
dc.date.accessioned | 2010-05-03T00:43:56Z | |
dc.date.available | 2010-05-03T00:43:56Z | |
dc.date.issued | 2009-12-15 | |
dc.date.submitted | 2009 | |
dc.identifier.other | http://dissertations.umi.com/ku:10695 | |
dc.identifier.uri | http://hdl.handle.net/1808/6177 | |
dc.description.abstract | The thesis details the development of a decarboxylative synthesis of aryl ethers using a relatively new Iron catalyst and a novel decarboxylative coupling of coumarins catalyzed by palladium. Aryl allyl carbonates underwent facile decarboxylative coupling in presence of a new iron catalyst. The allylation is found to be regioselective rather than regiospecific. This suggests that the allylation proceeds through π-allyl iron intermediates in contrast to related allylations of carbon nucleophiles that proceed via σ-allyl complexes. The reason we looked at iron as a catalyst was to offset the cost of expensive palladium catalyst usually used in these types of reactions. The second project involved allyl esters of 3-carboxylcoumarins, which underwent facile decarboxylative coupling at just 25−50 °C in moderate to good yields. This represents the first extension of decarboxylative C−C bond-forming reactions to the coupling of aromatics with sp3-hybridized electrophiles. Finally, the same concept can be applied to the sp2−sp3 couplings of pyrones and thiocoumarins. A variety of biologically important heteroaromatics can be readily functionalized without the need for strong bases or stoichiometric organometallics that are typically required for more standard cross-coupling reactions. | |
dc.format.extent | 111 pages | |
dc.language.iso | EN | |
dc.publisher | University of Kansas | |
dc.rights | This item is protected by copyright and unless otherwise specified the copyright of this thesis/dissertation is held by the author. | |
dc.subject | Organic chemistry | |
dc.subject | 3-allyl coumarins | |
dc.subject | Decarboxylation | |
dc.subject | Hieber anion | |
dc.subject | Iron catalysis | |
dc.subject | Prenylation | |
dc.subject | Sp2-sp3 coupling | |
dc.title | Iron-catalyzed decarboxylative cross coupling reactions and palladium-catalyzed sp2-sp3 coupling of coumarins. | |
dc.type | Thesis | |
dc.contributor.cmtemember | Flynn, Daniel | |
dc.contributor.cmtemember | Malinakova, Helena C. | |
dc.thesis.degreeDiscipline | Medicinal Chemistry | |
dc.thesis.degreeLevel | M.S. | |
kusw.oastatus | na | |
kusw.oapolicy | This item does not meet KU Open Access policy criteria. | |
kusw.bibid | 7079118 | |
dc.rights.accessrights | openAccess | |