CuII/TEMPO‐Catalyzed Enantioselective C(sp3)–H Alkynylation of Tertiary Cyclic Amines through Shono‐Type Oxidation

A novel strategy for asymmetric Shono‐type oxidative cross‐coupling has been developed by merging copper catalysis and electrochemistry, affording C1‐alkynylated tetrahydroisoquinolines with good to excellent enantioselectivity. The use of TEMPO as a co‐catalytic redox mediator is crucial not only for oxidizing a tetrahydroisoquinoline to an iminium ion species but also for decreasing the oxidation potential of the reaction. A novel bisoxazoline ligand is also reported.