New Chemistry of Hydroxyla Mines

This thesis consists of the exploration of a novel oxygenation procedure and its applicability in the preparation of synthetically useful compounds. Chapter 1 provides a review of methods for the preparation of TV-aryl hydroxylamines. Chapter 2 focuses on the development o f a novel a-oxygenation procedure. It describes work previously carried out within the group and continues with exploration of the scope of the transformation. It describes the development of a novel family o f reagents which are synthesised by one of three methods. Chapter 3 describes the first method for the direct introduction o f a carbamate and carbonate functionality ato a carbonyl group by modification of our generic reagent. Additionally, it explores how by simple variation o f the reaction medium oxazolidinone heterocycles can be accessed. Chapter 4 examines the use of the a-oxygenation procedure followed by reduction and reductive animation protocols to synthesis 1,2 -mono protected diols and 1,2-amino alcohols. Chapter 5 discusses an investigation into the design and synthesis of a number of precursors to hydroxylamine reagents with the potential to introduce a phosphonate group a -to a carbonyl functionality. Finally, Chapter 6 concentrates on the development o f conditions for coupling hydroxylamines to aryliodides. It describes the preparation of a family o f hydroxylamine reagents withdifferent protecting groups on both the nitrogen (Boc) and oxygen (methyl, benzyl, tetrahydropyran), to couple into the aryliodide using copper iodide. It examines the scope of the reaction by showing the use o f substrates with varying functionalities (electronwithdrawing, electron donating, aldehydes, esters, ketones, halides) in the para, meta and ortho positions of the aryliodide. \a brief in vestigation using the rearrangement strategy to access ortho hydroxyl anilines whilst utilising this coupling methodology is also examined.