Catalytic enantioselective synthesis of oxindoles and benzofuranones bearing a quaternary stereocenter and reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation
Name
59133112-MIT.pdf
Description
Full printable version
Size
11 MB
Format
Adobe PDF
Checksum (MD5)
39ec5c2b4b2fe4429db0bf71cf544363
Author(s)
Hills, Ivory Derrick, 1977-
Advisor(s)
Gregory C. Fu.
Alternative Title
Reactions of palladium bisphosphine complexes relevant to catalytic C-C bond formation
Date Issued
2004
Publisher
Massachusetts Institute of Technology
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.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
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.
Persistent DSpace Link
