Cobalt complexes of chiral pyrox ligands catalyzed enantioselective
reductive couplings of nonconjugated iododienes with aryl iodides
or alkenyl bromides. The reaction enabled stereoselective syntheses
of 5–7-membered azacycles carrying quaternary stereocenters.
Mechanistically, cross-electrophile selectivity originated from selective
coupling of alkylcobalt(I) complexes generated after cyclization with
aryl iodides.