New asymmetric bis(oxazoline) (Box) ligand bearing amide group at the oxazoline 4-position, ( S, S)-2,2′-methylenebis(4- tert-butylcarbamoyl-2-oxazoline) ( 1S ), was designed and synthesized for selective catalytic reaction. The crystal structure of the ternary copper complex, consisting of 1S and N-benzoyl-N-phenyl-hydroxylamine, demonstrated interligand interactions, such as hydrogen bonding and CH- π interaction. Catalytic performance of the copper complex with 1S was investigated for an asymmetric Diels–Alder reaction using benzylidene-2-acetylpyridine and 1,3-cyclohexadiene (CHD). The reaction product was enantio-pure endo-(pyridin-2-yl)(3-phenylbicyclo[2,2,2]oct-5-ene-2-yl)methanone (BPCD), of which crystal structure was analyzed by the X-ray method. No stereo- and enantio-isomer of BPCD was detected by chiral HPLC analysis. Introduction of hydrogen bonding site into 1S can promote the Diels–Alder reaction even though using poor reactive CHD. Without 1S , this reaction did not give any product. Addition of 2-propanol to this reaction system inhibited the formation of BPCD, indicating that the designed interligand interaction sites, especially hydrogen bonding, play an important role for catalytic performance.