Cu(II)/TEMPO‐Catalyzed Enantioselective C(sp3)–H Alkynylationof Tertiary Cyclic Amines via 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 enantioselectivities. 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 diminishing the oxidation potential of the reaction. A novel bisoxazoline ligand is also reported.