This project is focused on the transformation of heterocycles by exploiting their
interaction with oxygen in air as a means to construct C–C bonds via radical addition.
Chapter one introduces fundamental information about radical reactivity, C–H bond
transformations and aerobic C–H activation work. Furthermore, the reactions of radical
acceptors used in this thesis are introduced alongside current methods for
functionalising heterocycles. Chapter two describes the research and development
section of this work, where an optimised reaction is developed for the C–C bond
formation of heterocycles via an aerobic oxidation pathway. Alkynyl hypervalent iodine
and acetylenic triflone radical acceptors are shown to be compatible with differing
success in the designed reaction conditions. Following this, exemplification of the
alkynylation reaction is demonstrated by reaction scope studies for both the
heterocycles and radical acceptors. The method was also shown to be compatible with
vinyl triflones allowing access to vinyl heterocycles in one step. The use of the
products formed was demonstrated by novel transformations to generate privileged
scaffolds and fundamental building blocks of varying oxidation levels. Mechanistic
studies are carried out to confirm both the aerobic and radical nature of the developed
reaction conditions. Future directions are also highlighted as a result of the findings in
this thesis, finally the last chapter contains the experimental results and
characterisations of compounds mentioned within the thesis.