Electroorganic synthesis mediated by vitamin B12 derivatives has been developed in nonaqueous media. Especially, amphiphilic heptamethyl cobyrinate with a high solubility in various organic solvents was used in various kinds of electroorganic syntheses based on enzymatic function. Electrolysis of an organic halide catalyzed by the B12 model complex provided dechlorinated products under anaerobic conditions, while the electrolysis under aerobic conditions afforded oxidized products such as an ester and amide with dechlorination. Electrochemical reductions of an alkene and alkyne were also catalyzed by the B12 model complex at less negative applied potentials than those of the alkene and alkyne reductions. A bioinspired intermediate, expected as a cobalt–hydrogen complex, should be formed and catalyze the reaction.
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