Synthesis of natural and unnatural products by elaboration of alpha-chloroaldehydes

Date created: 
2017-04-21
Identifier: 
etd10114
Keywords: 
Synthesis
Natural product
Preussin
Chlorohydrin
Pheromone
Abstract: 

Fitting broadly under the category of target-oriented synthesis of complex organic molecules, the work described in this document pertains primarily to exploiting the facile organocatalytic synthesis of enantiomerically enriched α-chloroaldehydes, drawing out their potential through conversion into 1,2-chlorohydrins, and exploring the means by which these substances may be coerced to undergo intramolecular cyclization involving a nitrogen nucleophile. Specific targets and methodology include a successfully completed synthesis of the natural product (+)-preussin and similarly substituted pyrrolidines through the reductive annulation of β-iminochlorohydrins, a formal synthesis of (-)-swainsonine and related alkaloids through a related intramolecular cyclization strategy, and the synthesis and structural analysis of a carbocyclic mechanism-based inactivator of a glycoside hydrolase. As a secondary focus, this thesis also describes the isolation, structural elucidation, and testing of the long-range sex pheromone of the strepsipteran Xenos peckii, which was ultimately determined to be (7E,11E)-3,5,9,11-tetramethyltridecadienal, and of the chemical constituents of the bed bug (Cimex lectularius) aggregation pheromone, which were ultimately determined to be dimethyl disulfide, dimethyl trisulfide, (E)-2-hexenal, (E)-2-octenal, 2-hexanone, and histamine.

Document type: 
Thesis
Rights: 
This thesis may be printed or downloaded for non-commercial research and scholarly purposes. Copyright remains with the author.
File(s): 
Senior supervisor: 
Robert Britton
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.
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