Diels–Alder reactions of alkyl-substituted dienes with acrylonitriles give good yields and endo-selectivities if catalyzed by (organo)aluminum, (organo)boron or gallium halides. The activity of these group IIIa Lewisacids in this reaction correlates with the coordination strength of their nitrile complexes, which deactivate Lewisacids sufficiently, so that the subsequently added diene partner undergoes