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The Asymmetric synthesis of 2-epi-Prevezol C and the diastereoisomers of Quercivorol
thesis
posted on 2017-01-19, 03:08 authored by Blair, MichaelThe brominated secondary metabolites isolated from the polar fractions of the macroalga
Laurencia Obtusa (Lamoroux), termed ‘Prevezols’ posses cytotoxic properties against a
range of human carcinoma lines. These novel diterpenes contain unique molecular
architectures with an incredibly rare and challenging syn-bromohydrin motif, to date
unaddressed via total synthesis. This dissertation discloses the synthesis of the
diterpene framework of Prevezol C, via a stereoconvergent allylic alkylation strategy of
two monoterpene chirons, derived from the optically pure commercial mixture of cis- and
trans- limonene oxide. The first part of this thesis is concerned with the separation and
isolation of both the cis- and trans-limonene oxide isomers via a hydrolytic kinetic
separation, to the corresponding limonene trans- diaxial and -diequatorial diols (Chapter
2), which are implemented as part of the synthesis of the 2-bromo epimer of Prevezol C (Chapter 3, Part 1). A novel free radical hydrodebromination strategy (Chapter 3, Part 2)
was successfully employed as a means of accessing the naturally occurring synbromohydrin
relationship found in the Eastern domain of the Prevezols, and several
other secondary metabolites derived from the red algae species of Laurencia. Finally, a
second total synthesis of the major and minor constituents of the ambrosia beetle
Platypus quercivorus was also achieved (Chapter 4) via a palladium catalysed
deoxygenation strategy of the limonene trans-diaxial and -diequatorial diols.
History
Campus location
AustraliaPrincipal supervisor
Kellie TuckYear of Award
2009Department, School or Centre
ChemistryCourse
Doctor of PhilosophyDegree Type
DOCTORATEFaculty
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