Having established that piperine is both electrochemically active and has multiple oxidation events, we then employed our established protocols for Shono-type and Oxa-Shono-type oxidations. Piperine was reacted under electrochemical conditions and the series of products resulting were analysed by LC-MS (Scheme 1 and Figure ). Using MS fragmentation patterns (Figure ), and via comparison with related electrochemical and hepatocyte incubation data, It should be noted that piperine exists a Z,Z-conjugated alkene isomer but upon electrochemical reaction E,Z and/or Z,E-isomers form as detected by thin-layer chromatography (TLC) and LC-MS analysis (see supporting information) from a radical isomerism reaction in situ. A summary of the overlap between methods (phase II electrochemical and hepatocyte incubation of piperine) and novel metabolites with this work are shown in Table .