Thesis-2005-Wyatt.pdf (5.46 MB)
Download fileNew routes to highly functionalised compounds from vinylcyclopropanes
thesis
posted on 2018-07-27, 11:40 authored by Elisabeth J. WyattStudies towards the development of a novel methodology have been achieved. A
Palladium-catalysed [3 + 2] cycloaddition is described herein. Doubly activated
vinylcyclopropanes have been ring opened with palladium (0) and the resulting
zwitterionic π-allyl palladium species have participated in a nucleophilic addition with
activated carbonyl moieties to construct tetrahydrofurans as a mixture of
diastereoisomers. The palladium-catalysed [3 + 2] cycloaddition has shown to be
successful with ketone moieties activated by an adjacent electron-withdrawing group
such as ethyl esters in a range of α-keto esters, and amides in a range of substituted
isatins (scheme 1). The reaction boasts good yields and the stereochemical preference
of the reaction has shown to be dependent on the choice of reaction solvent. [Illustration omitted.] The reaction has shown to be successful on application to the intramolecular mode to
form a bicyclic heterocycle (scheme 2). [Illustration omitted.] The methodology has been successfully incorporated towards the synthesis of the
natural product monocerin.
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Department
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