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Computational Insight into Homogeneous Organopalladium Catalysis


Keith, John Andrew (2008) Computational Insight into Homogeneous Organopalladium Catalysis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/FAS9-DV26.


An investigation of modern computational simulation techniques and their results in describing two notable organopalladium reactions are discussed. First, a methodology for computational quantum chemistry simulations of homogeneous catalysis is presented. We find that through careful consideration of electronic and thermodynamic energy contributions, practical methods are available to accurately study complicated reaction mechanisms and to make educated predictions about their chemistry. We apply this technique to develop the first full analysis of the Wacker Process, olefin oxidation by PdCl2 catalysts, effectively uniting nearly 50 years of research into one mechanistic model. Key findings include the identification of competitive rate determining steps that are dependent on ion concentrations and the inaccessibility of [beta]-hydride elimination during product formation. The second analysis addresses the unique performance of the enantioselective Tsuji-allylation reaction, a reaction the great potential in the fields of asymmetric catalysis and natural product synthesis. In this reaction, calculations point towards enantioselectivity determined after the rate determining step. Intriguingly, we find that C-C coupling is facile in a variant to canonical reductive elimination containing characteristics of both reductive cheletropic and Claisen rearrangements. Lastly, a model is presented to direct improved catalyst design. In total, this dissertation presents an outline for practical quantum chemical simulation of complicated and elaborate organopalladium reactions.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Computational chemistry; Enantioselective Tsuji Allylation; implicit solvation; inorganic ligand exchange reactions; Wacker Process
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Goddard, William A., III
Thesis Committee:
  • Stoltz, Brian M. (chair)
  • Gray, Harry B.
  • Bercaw, John E.
  • Goddard, William A., III
Defense Date:21 September 2007
Non-Caltech Author Email:john.keith (AT)
Record Number:CaltechETD:etd-05012008-092352
Persistent URL:
Keith, John Andrew0000-0002-6583-6322
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:1565
Deposited By: Imported from ETD-db
Deposited On:20 May 2008
Last Modified:18 Dec 2019 22:22

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