Reaction of (Z)‐1,2‐bis(methoxycarbonyloxy)but‐2‐ene (2) with various N,N‐bis(arylsulfonyl)‐o‐phenylenediamines 1 was catalyzed by a palladium complex associated with chiral ligands to give optically active 1,4‐bis(arylsulfonyl)‐1,2,3,4‐tetrahydro‐2‐vinylquinoxalines 3 with up to 62% ee. The use of (S)‐MeOBIPHEP as the chiral ligand and N,N‐bis(p‐tolylsulfonyl)‐o‐phenylenediamine (1i) as the nucleophile led to the highest ee at 25 °C, regardless of the solvent used. The enantioselectivity of the cyclization is strongly affected by the nature of the substituents at the nitrogen atom.