The synthesis of 3-amino-8-azachromans and 3-amino-7-azabenzofurans derivatives is reported. The synthetic strategy is based on an inverseelectrondemandDiels–Alder approach, which employs 1,2,4-triazines that are judiciously substituted with amino alkynols. This approach permits the variation of the substituent on the aromatic core and on the amine moiety, as well as of the size of the nonaromatic