The proposed mechanism suggests that the efficiency of the annulation process is dictated by the formation of a final product that cannot deliver efficiently an α-aminoakyl radical due to an unfavorable (or less favorable) deprotonation step. This may explain the difficulties and low yield observed in the annulation of azepanes leading to [4. (to form 8e, Scheme 7) were more difficult than those with electron-poorer systems. They required much longer reaction times and, in the case of 1d, the use of a slightly stronger base. This indicates that the critical step of the process is probably not the amine oxidation but rather the deprotonation of the radical cation. Calculations showed that the more stable para-methoxyphenyl substituted radical cation RC1d is also much less acidic (pKa = +57.1 (DCE)/+14.4 (H2O)) than RC1a (pKa = +51.4