The first enantioselective dearomatizative spirocyclization of 1-hydroxy-N-aryl-2-naphthamide derivatives has been accomplished by chiral organoiodine catalysis to stereoselectively create an all-carbon stereogenic center, providing a straightforward approach to access spirooxindole derivatives in good yields and with high to excellent levels of enantioselectivity. Chiral hypervalent phenyl-λ(3) -iodanes generated in situ from the oxidation of the chiral phenyl iodine actually participate in the asymmetric oxidative dearomatizative spirocyclization reaction.

An asymmetric organocatalytic direct C-H/C-H oxidative coupling reaction of N(1),N(3)-diphenylmalonamides has been well established by using chiral organoiodine compounds as catalysts, wherein four C-H bonds were stereoselectively functionalized to give structurally diverse spirooxindoles with high levels of enantioselectivity. More importantly, the findings indicated that chiral hypervalent organoiodine reagents can serve as alternative catalysts for the creation of enantioselective functionalization of inactive C-H bonds.

The unprecedented combination of a palladium(ii) complex with a chiral Bu-QUOX ligand and a chiral phosphoric acid enables the highly efficient asymmetric oxidative tandem cyclization reaction, providing a straightforward method to access chiral 6,5-bicyclic aza-heterocycles in moderate to good yields and with excellent enantioselectivities.