Intramolecular acceleration effect of a tosylamide group on the electrochemical oxidation of N-α-silylalkyl amides

Abstract

In electrochemical oxidation, N-alkyl-N-α-silylalkyl (N-tosyl)amino acid amides react faster than N-alkyl-N-α-silylalkyl aliphatic amides. This phenomenon is due to the two roles of the tosylamide moiety. One is the assistance in release of the silyl cation by the tosylamide moiety to transform the cation radical, which possesses a higher oxidation potential, to the radical which possesses a lower oxidation potential. Another is the stabilization of the cation radical by the coordination of the tosylamide moiety to the positively charged silyl atom of the cation radical to shift the equilibrium of the first one-electron oxidation to the more stable side.