To provide a Diels Alder reaction catalyst which contains an -(N-acylamino) acrolein or an -(N,N-diacyl amino) acrolein as a dienophile and is best-suited for an asymmetric Diels Alder reaction.

An -phthalimide acrolein (0.25 mmol) is added to a solution obtained by solving chiraltriamine (0.025 mmol) represented by formula and pentafluorobenzene sulfonic acid (0.069 mol (2.75 equiv)) in 0.25 mL solvent. Next, a 2,3-butadiene (0.3 mmol) is added to the solution by dripping. After the lapse of a specified reaction time, the corresponding cyclized addition product can be obtained in a high yield and high excess enantiomorph ratio.