A challenging direct asymmetric catalytic aerobic oxidative cross‐coupling of 2‐naphthylamine and 2‐naphthol, using a novel CuI/SPDO system, has been successfully developed for the first time. Enantioenriched 3,3′‐disubstituted NOBINs were achieved and could be readily derived to divergent chiral ligands and catalysts. This reaction features high enantioselectivities (up to 96 % ee) and good yields (up to 80 %). The DFT calculations suggest that the F–H interactions between CF3 of L17 and H‐1,8 of 2‐naphthol, and the π–π stacking between the two coupling partners could play vital roles in the enantiocontrol of this cross‐coupling reaction.

2‐Bromoanilines are also efficient substrates for this reaction, though they are less reactive than 2‐iodoanilines and give slightly lower yields.

Copper‐catalyzed oxidative radical alkylarylation using N‐arylacrylamides and azo compounds (II) or (VIII) produces oxindoles through a cascade addition/C(sp2)—H cyclization process.