(DCE)/+8.7 (H2O)). The electrochemical investigation of 1d by cyclic voltammetry provided a quasi reversible oxidation wave in the absence of added base (Figure , A) whilst the simple Nphenylpyrrolidine 1a produced irreversible oxidation event (see supporting information). The addition of cesium pivalate drastically changed the cyclic voltammogram of 1d and two oxidation waves were observed (Figure ). A first irreversible oxidation wave appeared at a slightly lower oxidation potential than the oxidation event of the amine alone. This shift of potential relative to the cyclic voltammogram in the absence of base is attributed to an oxidation event of the amine interacting with cesium pivalate, possibly a proton-coupled electron transfer (PCET) process. The second wave, The hypothesis that the reactions stop at the bicyclic stage due to inefficient deprotonation of the bicyclic radical cations offers the opportunity to run a more complex reaction process involving a bisannulation process starting from a tertiary acyclic aniline derivative and ending with an oxidationresistant bicyclic system. This assumption was tested with N,N-dimethyl aniline. In the presence of 2.2 equivalents of the allylic acetate radical trap added in two portions (at the beginning of the reaction and after 15 minutes), the product of bis-annulation product 14 was isolated in 13% yield with good stereocontrol. By starting from N-methyl-N-trimethylsilylmethylaniline, the yield for the formation of 14 could be improved to 22%. In this process, the product of the first annulation (Scheme 12, blue bond formation) leads to a piperidine derivative that can further react via a second annulation process (Scheme 12, red bond formation) to produce 14. All attempts to stop at the piperidine stage gave complex inseparable mixture of products.