Diels–Alder reaction
Similarly, electron-rich styrenes participate in intra- or intermolecular Diels–Alder cyclizations via a radical cation mechanism. [Ru(bipy)3]2+ was a competent catalyst for intermolecular, but not intramolecular, Diels–Alder cyclizations. This photoredox-catalyzed Diels–Alder reaction allows cycloaddition between two electronically mismatched substrates. The normal electronic demand for the Diels–Alder reaction calls for an electron-rich diene to react with an electron-poor olefin (or "dienophile"), while the inverse electron-demand Diels–Alder reaction takes place between the opposite case of an electron-poor diene and a very electron-rich dienophile. The photoredox case, since it takes place by a different mechanism than the thermal Diels–Alder reaction, allows cycloaddition between an electron-rich diene and an electron-rich dienophile, allowing access to new classes of Diels–Alder adducts.