The addition of O-H and N-H bonds across carbon-carbon double bonds offers a direct way
of synthesising a variety of organic molecules. These reactions have attracted considerable
interest in academic research and the chemical/pharmaceutical industry in recent years due
to its atom economy. Nevertheless, there remains a considerably challenge to control the
regioselectivity and the stereoselectivity of this reaction.
This PhD thesis describes the investigation into the discovery and development of a general
method for catalytic hydroamination (HA), hydroalkoxylation and hydrooxyacylation of
olefins. Air- and moisture-stable transition metal catalysts were the main focus of this
study.
The introductory Chapter provides an overview of recent advances in N-H addition
reactions involving late transition metal catalysts.
In Chapter 2, rhodium and ruthenium complexes were examined as catalysts for the
addition of N-H bonds to alkenes. The combination of (RuCl2)n/dppb/AgOTf generated a
catalyst effective for the addition of methyl carbamate to norbornene in a modest yield.
Copper (II) trifluoromethanesulfonate was discovered to be an efficient catalyst for the
addition of carboxylic acids, phenols and alcohols to norbornene. A selection of norbornyl
esters and ethers were formed in good to excellent yields.
In the following Chapter, the combination of copper (II) trifluoromethanesulfonate and
diphosphine ligands was successfully applied to the addition of sulfonamides and
carbamates to vinylarenes, 1,3-dienes and norbornene in good to excellent yields.
In Chapter 4, the intramolecular hydroamination reaction was developed. The synthesis of
several acyclic precursors were described, along with attempts to cyclise them. The chapter
ends with the attempted synthesis of tricyclic molecules using a palladium-catalysed
methodology.
The last Chapter contains experimental procedures and characterisation data of all the
compounds synthesised during the course of this project
