Electrochemical C(sp3)-H Functionalization of γ-Lactams Based on Hydrogen Atom Transfer.

We describe the electrochemical α-amidoalkylation of γ-lactams based on transition-metal-free cross-coupling via hydrogen atom transfer. The highly selective hydrogen atom transfer process allows for a broad substrate scope including both inter- and intramolecular reactions. Also, the construction of quaternary centers was realized by a double hydrogen atom transfer protocol to afford spirocycles. Detailed mechanistic studies including experimental and computational studies are provided to support the reaction pathway.

Metal-Free Synthesis of Indolopyrans and 2,3-Dihydrofurans Based on Tandem Oxidative Cycloaddition.

The synthesis of versatile scaffold indolopyrans based on C-C radical-radical cross-coupling under metal-free conditions is described. The reaction involving single electron transfer between coupling partners followed by cage collapse allows highly selective cross-coupling while employing only equimolar amounts of coupling partners. Moreover, the mechanistic manifold was expanded for the functionalization of enamines to give the stereoselective synthesis of 2,3-dihydrofurans. This iodine-mediated oxidative coupling features mild conditions and fast reaction kinetics.

Electrosynthesis of Dihydropyrano[4,3-b]indoles Based on a Double Oxidative [3+3] Cycloaddition.

Oxidative [3+3] cycloadditions offer an efficient route for six-membered-ring formation. This approach has been realized based on an electrochemical oxidative coupling of indoles/enamines with active methylene compounds followed by tandem 6π-electrocyclization leading to the synthesis of dihydropyrano[4,3-b]indoles and 2,3-dihydrofurans. The radical-radical cross-coupling of the radical species generated by anodic oxidation combined with the cathodic generation of the base from O2 allows for mild reaction conditions for the synthesis of structurally complex heterocycles.