The hetero Diels-Alder reaction of enamino ketone 1 with the vinyl ethers 7-11 leading to the dihydropyrans 12a-e and 13a-e is studied in dichloromethane under high pressures up to 7 kbar. The kinetics is measured by on-line FT-IR spectroscopy up to 3 kbar. For the first time individual rate coefficients kcis and ktrans have been determined. Pressure-averaged activation volumes, ΔV‡, for the overall reaction leading to the formation of the two diastereomers in dichloromethane solution between -(19.1 ± 1.7) and -(25.4 ± 1.6) cm3 mol-1 are measured. The corresponding activation enthalpies, ΔH‡, are between (62.2 ± 1.6) and (76.3 ± 3.6) kJ mol-1. The cycloaddition shows a remarkable increase in diastereoselectivity in favour of the cis adducts 12a-e toward higher pressure. The pressure-averaged differences in activation volume, ΔV‡, for the two reaction pathways leading to cis and trans diastereomers are found to be between -(4.5 ± 0.3) and -(6.9 ± 0.7) cm3 mol-1. The corresponding differences in activation enthalpy, ΔΔH≠, are between -(4.7 ± 1.4) and -(9.9 ± 1.6) kJ mol-1. Combination of the overall rate coefficient k = kcis + ktrans for the reaction leading to the two diastereomers with the measured product ratio, ccis/ctrans, which is identified with the ratio of the rate coefficients kcis/ktrans, yields the individual coefficients kcis and ktrans. The rate coefficient kcis is strongly influenced by the steric demand of the substituents on both diene and dienophile whereas ktrans varies to a smaller extent, and the observed changes appear to be mainly due to the electronic properties of the substituents.