Reacivity of 2-chloro- and 2-(tosyloxy)cyclohexanones towards anions electrogenerated at carbonium and nitrogen atoms. Electrochemically induced Favorskii rearrangement

The reactivity of carbonium and nitrogen anions generated by cathodic reduction of 6, 7 and 8 or by deprotonation (by means of electrogenerated bases) of 9 and 10 towards α-substituted ketones 1 and 2 has been studied. The reaction products 5b-d, 4b and 3 are formed according to Favorskii rearrangement, substitution and formal reduction mechanisms respectively. Also, in most cases, the reaction path appears to be driven by the applied electric potential. Concerning the Favorskii rearrangement undergone by 1 and 2 under electrochemical conditions, it can also been induced by nitrogen (Ph-NH-N-Ph) and carbonium (CH3COCHCO2Et) anions, which until now have never been used in this kind of reaction.