Oxidative Coupling of Nitromethane

Oxidation of tertiary amino derivatives under different conditions generates the corresponding iminium ion which readily reacts with methanenitronate anion leading to a nitramine compound. Molecular oxygen, peroxides and peracids are widely used for this puropse in transition metals catalyzed reactions. Conversely, organic oxidants such as diacetoxyiodobenzene, DDQ and TEMPO are effective without the need of any added catalyst. Visible light photoinduced coupling reactions are emerging as a safe and environmental friendly alternative to the above cited procedures. Oxidation is provided by Ir and Ru organometallic complexes as well as organic sensitizers (Rose Bengal and Eosin Y) brought in their excited states by visible light irradiation. Utilization of nitromethyl radicals, obtained by oxidation of nitromethane with CAN, in addition reactions with electron-rich alkenes is limited to the synthesis of nitrosugar derivatives.