Electroreduction of Nitrocyclopropanes and Nitroaryl Cyclopropanes

The electrochemical behavior of the substituted nitrocyclopropanes 3 (n = 1) as well as of the nitrophenylcyclopropanes 7 (n = 1) have been studied at a Pt electrode by cyclic voltammetry, microcoulometry, and preparative electrolysis in DMF-(n-Bu)4PF6. Electroreduction of 8 consumes one electron to give radical anion 8•−, which undergoes a homolytic C-N bond cleavage leading to the formation of the corresponding cyclopropyl radical and the nitrite ion. Electroreduction of 11 consumes 2 electrons. The radical anion 11•− is formed first followed by C-C bond cleavage (homolytic and/or heterolytic) of the cyclopropane ring leading to a distonic radical anion 5•−. The latter is reduced to the corresponding distonic dianion, which is protonated in the aqueous work up.