Investigations into Aryne chemistry
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Date
22/06/2012Author
Cant, Alastair Alexander
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Abstract
The first project in this thesis describes our research reacting arynes with tertiary allyl amines to
generate functionalised anilines via a benzyne induced aza-Claisen reaction. This process works
in good to excellent yields and the methodology can be further applied to make benzannulated
medium sized ring amine systems. The second project covered in this thesis details our studies in the generation of benzyne from
benzoic acid. This process utilises palladium catalysis involving an ortho C-H activation of
benzoic acid which generates a 5 membered palladacycle. This palladacycle then spontaneously
decomposes with heat to generate palladium bound benzyne and carbon dioxide. The yield of
benzyne was monitored by observing the amount of triphenylene formed in the process. Further
synthetic applications in this process were limited, but it was shown that the benzyne could be
reacted with alkynes to generate phenanthrene and naphthalene products. The third project in this thesis details our work on the insertion of benzyne into the C–S bond of
thioesters. Using palladium catalysis and an o-trimethylsilylphenyl triflate benzyne precursor, a
variety of thioethers were produced. The yields for this reaction were moderate to good but it
was found that only aromatic substituents were tolerated on the thioester.