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dc.contributor.advisorStephen L. Buchwald.en_US
dc.contributor.authorHuang, Xiaohua, 1973-en_US
dc.contributor.otherMassachusetts Institute of Technology. Dept. of Chemistry.en_US
dc.date.accessioned2006-03-24T16:10:30Z
dc.date.available2006-03-24T16:10:30Z
dc.date.copyright2003en_US
dc.date.issued2003en_US
dc.identifier.urihttp://hdl.handle.net/1721.1/29639
dc.descriptionThesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.en_US
dc.descriptionVita.en_US
dc.descriptionIncludes bibliographical references.en_US
dc.description.abstractNew methods for Pd-catalyzed cross-coupling reactions of aryl halides or arenesulfonates are described. Key to the success of these transformations is the proper choice of ligand and reaction conditions. Palladium catalysts supported by bulky, monodentate phosphine ligands with a biaryl backbone or the bidentate ligand, Xantphos, effectively promote the formation of ca-aryl carbonyl compounds. Base-sensitive functional groups are better tolerated when a weak base, such as K3PO4, is used. One of the most difficult transformations in Pd catalysis, the intermolecular C-O bond formation between primary alcohols and electron-neutral or even electron-rich aryl halides, was effectively promoted by the use of a new generation of ligands, 3-methyl-2-di-t-butylphosphinobiaryl. The one-step synthesis of ligands from cheap starting materials, as well as the mild reaction conditions employed for the coupling reactions, enables the practical use of Pd catalysis to access aryl alkyl ethers for the first time. Continuing study of Pd-catalyzed C-N bond-forming processes using biaryl monophosphine ligands led to the discovery of a structural derivative of these ligands, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl. This ligand, in combination with a Pd source, produces a catalyst system with both a greater degree of activity and of stability than those that use our previous ligands. Substrates that were not amenable to Pd catalysis previously are reexamined using this new catalyst system, and excellent results are obtained.en_US
dc.description.statementofresponsibilityby Xiaohua Huang.en_US
dc.format.extent216 leavesen_US
dc.format.extent6636696 bytes
dc.format.extent6636505 bytes
dc.format.mimetypeapplication/pdf
dc.format.mimetypeapplication/pdf
dc.language.isoengen_US
dc.publisherMassachusetts Institute of Technologyen_US
dc.rightsM.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.en_US
dc.rights.urihttp://dspace.mit.edu/handle/1721.1/7582
dc.subjectChemistry.en_US
dc.titlePalladium-catalyzed C-C, C-N and C-O bond formationen_US
dc.title.alternativePalladium-catalyzed carbon-carbon, carbon-nitrogen and carbon-oxygen bond formationen_US
dc.typeThesisen_US
dc.description.degreePh.D.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Dept. of Chemistry.en_US
dc.identifier.oclc53399636en_US


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