The catalytic enantioselective desymmetrizing bromoaminocyclization of prochiral cyclohexa-1,4-dienes has been achieved by using chiral anion phase-transfer catalysis, providing a range of enantioenriched cis-3a-arylhydroindoles bearing an all-carbon quaternary stereocenter in good yields (up to 78%) and excellent enantioselectivities (up to 97% ee). Furthermore, the potential application of this methodology to natural product total synthesis was demonstrated by the asymmetric synthesis of (+)-Mesembrane.