Abstract A wide range of cyclohexadienones has been synthesised in order to study their reactivity and their regio-and stereoselectivity with the enantiopure diene 1 under high- pressure conditions. Computational investigations were used to point out some parameters which affect the reactivity in this high chiral discrimination process. In addition, the resulting [4+ 2] cycloadducts allowed the preparation of new polyfunctional cyclohexenone ...