A novel catalytic asymmetric reaction is reported where the regiodivergent desymmetrisation of meso-azabicycloheptene via allylic oxidation using a single chiral copper catalyst produced two different, enantioenriched structural isomers in high optical purity starting from a single compound. The enantioselectivity of the two structurally isomeric compounds was enriched to >99.5% ee after derivatization.