2026-09-19T18:26:01Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/286992022-01-13T07:54:21Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Gregory C. Fu.
Hills, Ivory Derrick, 1977-
Massachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2005-09-27T17:50:40Z
2005-09-27T17:50:40Z
2004
2004
http://hdl.handle.net/1721.1/28699
59133112
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.
Includes bibliographical references.
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.
by Ivory Derrick Hills.
Ph.D.
376 p.
11485862 bytes
11537807 bytes
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Massachusetts Institute of Technology
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http://dspace.mit.edu/handle/1721.1/7582
Chemistry.
Catalytic enantioselective synthesis of oxindoles and benzofuranones bearing a quaternary stereocenter and reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation
Reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation
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