The development of efficient methods for the synthesis of highly functionalized chiral molecules is of great interest in organic chemistry. Given the ubiquity of nitrogen and oxygen containing compounds in nature and biologically relevant molecules, the direct asymmetric construction of C-N and C-O bonds becomes invaluable. While arylnitroso compounds are known sources of electrophilic nitrogen and oxygen, their use is inherently limited by their known toxicity and the difficulty of removing the N-aryl group for subsequent C-N bond forming reactions. Our group has focused on the use of nitrosocarbonyl intermediates which are generated in situ from substituted hydroxylamines and bear readily removable protecting groups on nitrogen. Nitrosocarbonyl intermediates are highly reactive and prone to decomposition using traditional stoichiometric oxidation processes. We postulated that the identification of a mild oxidation protocol would offer a marked improvement to known reaction platforms and facilitate the development of un-discovered synthetic transformations.

The context for developing nitrosocarbonyl chemistry will be provided through an overview of relevant nitroso compounds, with an emphasis on synthesis and reactivity. The discovery of the nitrosocarbonyl aldol reaction is a major component of this thesis, and this will be prefaced with a review on the state of the art in this area. The asymmetric nitroso ene reaction has long remained an elusive target in this area of research, and presented herein is an account of the first general asymmetric nitrosocarbonyl ene reaction, along with a proposed strategy to access enantioselective transformations with nitroso compounds.