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|Title: ||Rhodium carbenoid route to oxazoles|
|Authors: ||Doyle, Kevin J.|
|Issue Date: ||1994|
|Publisher: ||© Kevin James Doyle|
|Abstract: ||This thesis describes investigations by the author into the preparation of the oxazole
heterocyclic system, by the use of rhodium carbenoid methodology.
Chapter 1 is a review of the literature on the formation of oxazoles, by the reaction between
diazocarbonyl compounds and nitrites. The various conditions that have been employed in
the reaction are detailed, as well as developments into the understanding of its mechanism.
Chapter 2 reports the study into the preparation of 4-functionalised oxazoles. A series of 4-
benzenesulfonyloxazoles, oxazole-4-phosphates and oxazole-4-carbonitriles were prepared
by a rhodium(II)-catalysed reaction. The effect of varying the rhodium(II) catalyst on
oxazole formation is detailed. The oxazole-4-carbonitrile methodology was extended to form
bis-oxazoles. Attempts to extend this chemisiry towards tris-oxazoles is discussed.
Chapter 3 describes the synthesis of the oxazolylindole alkaloids pimprinine, pimprinethine
and WS-30581A. This was achieved by the reaction of tert-butyl 3-diazoacetylindole-1-
carboxylate with the appropriate nitrile, under rhodium(II) catalysis, followed by
deprotection. Studies into varying the substituents at the 2- and 4-positions of the oxazole
ring is described.
Chapter 4 relates investigations into the synthesis of the cytotoxic cyclic peptides,
diazonamide A and B, isolated from the ascidian, Diazona chinensis. These investigations
were centred on key skeletal features: an oxazolylindole moiety, an oxazole based around
(S)-valine and a functionalised benzofuranol. Model studies towards the oxazolylindole and
the valine oxazole sections were undertaken, utilising rhodium carbenoid methodology to
prepare the azote heterocycle. Formation of the benzofuranol model involved a one step
deprotection and cyclisation, the precursor being prepared via a Claisen rearrangement and an
Chapter 5 contains the experimental data, whilst Chapter 6 contains the references.|
|Description: ||A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy at Loughborough University.|
|Appears in Collections:||PhD Theses (Chemistry)|
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