Development of Electrochemical Processes for Nitrene Generation and Transfer

An electrochemical strategy for running nitrogen-transfer reactions on chemically inert anode
surfaces has been developed. The generation and trapping of highly reactive nitrene-transfer
reagents can be accomplished under mild conditions on platinum electrodes. The key factor that
accounts for the high levels of chemoselectivity in this process is the phenomenon of overpotential.
We have found that molecules that are similar in terms of propensity toward oxidation can be
differentiated on the basis of their affinity to a given electrode surface. Thereby, reactive species
can be selectively generated in the presence of acceptor molecules of interest. Specifically, a wide
range of structurally dissimilar olefins can be transformed into the corresponding aziridines in the
presence of N-aminophthalimide. Likewise, nitrene generation in the presence of sulfoxides leads
to their chemoselective transformation into the corresponding sulfoximines. In this paper we discuss
the underlying mechanistic foundation of these reactions.