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The first part of this paper deals with stereochemical studies related to the Diels-Alder reactions of 2-azadienes. 2-Azadienes could be readily prepared from carboxylic acid chlorides and imine derivatives. Their reactions with electron-poor dienophiles showed an interesting chemical dichotomy : cyclic dienophiles mainly yielded endo-adducts while acyclic dienophiles reacted with a high exo-selectivity. This selectivity could be further increased by using Lewis acids which are compatible withdoi:10.1351/pac199668010015 fatcat:dcoxfdvt6jc6xogmt6zpoeufjm