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Catalytic enantioselective synthesis of oxindoles and benzofuranones bearing a quaternary stereocenter and reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation

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dc.contributor.advisor Gregory C. Fu. en_US
dc.contributor.author Hills, Ivory Derrick, 1977- en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.date.accessioned 2005-09-27T17:50:40Z
dc.date.available 2005-09-27T17:50:40Z
dc.date.copyright 2004 en_US
dc.date.issued 2004 en_US
dc.identifier.uri http://hdl.handle.net/1721.1/28699
dc.description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004. en_US
dc.description Includes bibliographical references. en_US
dc.description.abstract In Part I the development of a new method for the construction of oxindoles and benzofuranones bearing quaternary stereocenters is discussed. A planar-chiral PPY derivative catalyzes the O-to-C acyl group migration (Black rearrangement) in a highly efficient and enantioselective manner. The utility of this method is further demonstrated by the formal total synthesis of the natural product aplysin. In Part II reactivity of bisphosphine palladium-complexes is discussed. It is shown that the oxidative addition of bisphosphine palladium-complexes bearing P(t-Bu₂)Me occurs through an SN2-type mechanism. This discovery allows us rationalize the difference in catalytic activity between Pd(P(t-Bu₂)Me)₂ and Pd(P(t-Bu₂)Et)₂ for the cross-coupling of alkyl electrophiles. The reductive elimination of H-X from bisphosphine palladium-hydride complexes is also discussed. The discovery that (P(t-Bu)₃)₂PdHCl undergoes facile reductive elimination in the presence of Cy₂NMe, while (PCy₃)₂PdHCl does not, is explained using X-ray crystal structures. These reactivity patterns may help to explain why Pd(P(t-Bu)₃)₂ is a much better catalyst than Pd(PCy₃)₂ for the Heck coupling of aryl chlorides. Finally, Part III describes preliminary work on a palladium-hydride catalyzed isomerization of allylic alcohols as well as initial attempts to study the mechanism of nickel-catalyzed cross-couplings of secondary alkyl-electrophiles. en_US
dc.description.statementofresponsibility by Ivory Derrick Hills. en_US
dc.format.extent 376 p. en_US
dc.format.extent 11485862 bytes
dc.format.extent 11537807 bytes
dc.format.mimetype application/pdf
dc.format.mimetype application/pdf
dc.language.iso en_US
dc.publisher Massachusetts Institute of Technology en_US
dc.rights M.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.uri http://dspace.mit.edu/handle/1721.1/7582
dc.subject Chemistry. en_US
dc.title Catalytic enantioselective synthesis of oxindoles and benzofuranones bearing a quaternary stereocenter and reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation en_US
dc.title.alternative Reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation en_US
dc.type Thesis en_US
dc.description.degree Ph.D. en_US
dc.contributor.department Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.identifier.oclc 59133112 en_US


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