Chapter One reviews aspects of the chemistry of allene oxides reported in the chemical
literature. The review is organised into three sections describing the available methods for
the preparation of allene oxides, the reactions of allene oxides and allene oxides in biological
Chapter Two discusses attempts to develop new methods for the generation and trapping of
allene oxides. Firstly, an unsuccessful attempt to employ a selenoxide elimination to generate
an allene oxide is described. This is followed by a section detailing an improved method for
the generation and in situ capmre of allene oxides with alcohols. Sodium alkoxides were
found to trigger elimination in β,y-epoxy-β-trimethylsilyl mesylates to afford allene oxides
and also act as the nucleophilic trapping component. This methodology was used to
synthesise a range of α alkoxyketones. Attempts to employ other nucleophiles in this process
are also discussed.
Chapter Three describes how the successful chemistry described in Chapter Two was
modified in order to generate and trap chiral, non-racemic allene oxides. The preparation of
homochiral β,y-epoxy-β-trimethylsilyl mesylates and their subsequent reaction with
potassium alkoxides at low temperature under aprotic conditions is described. The α;alkoxyketone
products were found to be of high enantiomeric excess and the absolute
configuration of the product was determined in one case. Finally, attempts to effect a threecomponent
coupling of an aIlene oxide, by reaction of an allene oxide with a nucleophile and
subsequently an electrophile, are discussed.
Chapter Four describes pioneering work towards a general method for the preparation of
methylene cyclic sulfites as potential allene oxide equivalents is presented. A series of such
compounds were prepared by reaction of α;-hydroxyketones with thionyl chloride and via
selenoxide elimination chemistry.
Chapter Five describes the detailed experimental work undertaken in this thesis.
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.