It has been established that a cationic gold(I)/axially chiral biaryl bisphosphine complex catalyzes asymmetric dearomatization of 1-aminonaphthalene derivatives by the intramolecular double C-C bond formation. Two different dearomatization products were obtained depending on the substituents on the benzyl groups at the alkyne termini.

A cationic gold(I)/axially chiral biaryl bis(phosphine) complex has been employed to catalyze the asymmetric dearomatization reactions of 1-aminonaphthalene derivatives through a C-C bond-forming reaction with electron-rich het-

The gold catalyzed asymmetric intramolecular C—C bond forming reaction of 1‐aminonaphthalene derivatives provides access to pentacyclic heterocycles with low to moderate enantioselectivities.