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


Other title
piperidine alkylation
lysergic acid
interrupted Nazarov
computational study
Type of item
Degree grantor
University of Alberta
Author or creator
Dunbar, Christine R
Supervisor and department
West, Frederick (Chemistry)
Examining committee member and department
Stryker, Jeffrey (Chemistry)
Tantillo, Dean (Chemistry)
Tuszynski, Jack (Physics)
Gibbs-Davis, Julianne (Chemistry)
Lowary, Todd (Chemistry)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
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.
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
Citation for previous publication
Y.-K. Wu, C. R. Dunbar, R. MacDonald, M. J. Ferguson, and F. G. West, “Experimental and Computational Studies on the Interrupted Nazarov Reactions: Exploration of Umpolung Reactivity at the α-Carbon of Cyclopentanones,” Journal of the American Chemical Society, 2014, 136, 14903-14911.C. R. Dunbar and F. G. West, “Diastereoselective N-Quaternization of Piperidines,” Canadian Journal of Chemistry, 2014, 10.1139/cjc-2014-0423.

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