Aromatic “Redox Tag”-assisted Diels–Alder reactions by electrocatalysis† †Electronic supplementary information (ESI) available: Additional figures, tables and general, experimental, theoretical and spectral information. See DOI: 10.1039/c6sc02117d Click here for additional data file.

Electrocatalysis was employed to promote Diels–Alder reactions between electronically mismatched substrates. A catalytic amount of electricity was enough to complete the overall reactions and GC-MS monitoring and CV measurements clearly illustrated the electrocatalytic nature of the reactions, which involve an EC-backward-E mechanism. The electrocatalytic Diels–Alder reactions were rationally designed based on the concept of redox tags. The results were supported by DFT calculations.