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Diastereomeric Piperidinium Salts: Their Preparation, Study, and Use in Synthesis

  • Author / Creator
    Dunbar, Christine R
  • Diastereomeric piperidinium salts were prepared as substrates for the Stevens [1,2]-rearrangement of ammonium ylides, the key step in a proposed synthetic route towards lysergic acid, a valuable compound in medicinal and synthetic chemistry. Because of unexpected reactivity seen in the alkylation of substituted piperidine derivatives to form the piperidinium salts, an analysis of the previous literature in this field was undertaken; literature experimental data was subjected to computational analysis to more fully understand the complexities of this reaction, as well as to find and demonstrate the utility of a suitable computational approach to this reaction. In addition to analyzing previously-reported data, new alkylation experiments were undertaken to broaden the known substrate scope of this reaction and to provide more recent data for computational analysis. This computational analysis was also applied to the formation of piperidinium salts in the original route towards lysergic acid, showing its applicability to known problems in synthesis. During the course of this computational research, many interesting mechanistic questions arose in other projects in the group; computational mechanistic work was undertaken in the context of an unusual interrupted Nazarov reaction, as well as in the nascent field of the reactivity of six-membered cyclic allenes.

  • Subjects / Keywords
  • Graduation date
    2015-06
  • Type of Item
    Thesis
  • Degree
    Doctor of Philosophy
  • DOI
    https://doi.org/10.7939/R3CK7S
  • License
    This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
  • Language
    English
  • Institution
    University of Alberta
  • Degree level
    Doctoral
  • Department
    • Department of Chemistry
  • Supervisor / co-supervisor and their department(s)
    • West, Frederick (Chemistry)
  • Examining committee members and their departments
    • Tantillo, Dean (Chemistry)
    • Gibbs-Davis, Julianne (Chemistry)
    • Lowary, Todd (Chemistry)
    • Tuszynski, Jack (Physics)
    • Stryker, Jeffrey (Chemistry)