Synthesis and Physical Organic Chemistry of C-Nitroso Compounds: C-Nitroso Ketones as Donors of Nitrosonium

Much of our knowledge regarding the biology of nitric oxide (NO), a key biological signaling molecule, has come from the use of synthetic agents that release NO or a redox-related species. Despite the proliferation of NO-donor complexes, rates of NO release and the redox state of the liberated NO from these compounds are neither predictable nor controllable to any practical extent. C-nitroso compounds comprise a unique class of NO donors from which the rate of NO release and the oxidation state of the liberated NO can be precisely controlled by the nature of the substituents geminal to the nitroso-bearing carbon. Furthermore the concentration of the active NO releasing agent (e.g. the monomeric nitroso species) is governed by the position of the dimer-monomer equilibrium, a process that is also sensitive to substitution. Thus the manifold through which these compounds release NO is highly dependent on the electronic character of the substituents about the nitroso bearing carbon.