Title page for ETD etd-08202002-151742


Type of Document Dissertation
Author Struss, John Anthony
Author's Email Address jstruss@ut.edu
URN etd-08202002-151742
Title New Methods for the Formation of Methyl Bearing Stereogenic Centers via Methylketene Dimerization and Free Radical Additions to Allyl Bromides
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Tanko, James M. Committee Chair
Brewer, Karen J. Committee Member
Carlier, Paul R. Committee Member
Castagnoli, Neal Jr. Committee Member
Deck, Paul A. Committee Member
Keywords
  • Allyl Bromide
  • Methylketene
  • Allyl Transfer
  • Siphonarienal
  • Asymmetric Synthesis
  • Free Radical
Date of Defense 2002-08-15
Availability unrestricted
Abstract
Two organic synthetic methods for the generation of methyl bearing chiral centers have been developed using: 1) dimerization of methylketene and 2) a free radical-based addition/elimination reaction involving allyl bromides. The first method, the asymmetric dimerization of methyl ketene, followed by an asymmetric aldol reaction and the appropriate functional group manipulations enabled us to construct the (2S, 4S, 6S) trimethylnonyl subunit found in the siphonariene class of natural products. The latter method explored the stereoselective potential of a free radical-based condensation reaction by examining compounds which are known to be able to support chiral auxiliaries and chiral Lewis acids. Additionally, substituent effect on the rates of this reaction were examined closely and found to be comparable to similar, previously examined systems. The synthetic utility, magnitude and scope of this reaction are discussed.

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