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TitleStudies on an organocatalytic synthesis of functionalized nitrocyclohexanones and (+)-lycoperdic acid
AuthorAdsool, Shubhangi V., 1979-
DescriptionThesis (M.Sc.)--Memorial University of Newfoundland, 2010. Chemistry
Paginationxiv, 146 leaves : ill.
SubjectAcetone; Addition reactions; Amino acids--Synthesis; Cyclohexanones--Synthesis; Nitroalkenes
Degree GrantorMemorial University of Newfoundland. Dept. of Chemistry
NotesIncludes bibliographical references.
AbstractA strategy for enantioselective double Michael addition reactions of acetone to nitroalkene 1 has been investigated. The feasibility of employing an enamine-mediated, organocatalytic route to functionalized cyclohexanones 2 was examined in this study (Scheme 1).* -- Simultaneously, in continuation with the Pansare group's interest in organocatalytic conjugate addition reactions, an organocatalytic, conjugate addition based synthesis of (+)-lycoperdic acid (10 ) was examined. Lycoperdic acid is an unusual amino acid isolated from a mushroom ( lycoperdon perlatum ). Its unique structure and potential glutamate receptor activity, makes it a challenging synthetic target. Our approach to lycoperdic acid is based on the enantioselective organocatalytic Mukaiyama-Michael addition of furan 5 to acrolein, mediated by catalysts 11 and 12 to provide the key butyrolactone 6 (Scheme 2). It is noteworthy that only a few examples of enantioselective organocatalytic Mukaiyama-Michael conjugate additions of furans related to 5 and β-substituted α, β-unsaturated aldehydes are known, and the use of acrolein as a Michael acceptor in these reactions has not previously been reported. Conversion of 6 to (S )-homocitric acid lactone (8 ) not only provided a new synthesis of this natural product enantiomer, and also established the stereochemistry of the Michael addition of 5 to 6. An organocatalytic α-amination of 6 using catalyst 12 provided 9 which is an advanced intermediate to lycoperdic acid.* *Please refer to dissertation for diagrams.
Resource TypeElectronic thesis or dissertation
FormatImage/jpeg; Application/pdf
SourcePaper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries
Local Identifiera3475056
RightsThe author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission.
CollectionElectronic Theses and Dissertations
Scanning StatusCompleted
PDF File(13.49 MB) --
CONTENTdm file name84624.cpd