Abstract: The reaction of substituted furans a-c and Danishefsky's diene which yield 5-benzofuranol derivatives has been studied using the hardness, the polarizability and the electrophilicity of the corresponding D-A primary adducts as global reactivity indexes. The main objective of this work is to investigate the power of these global indexes in predicting the major regioisomer. It has been demonstrated that both the hardness as well as the electrophilicity power of the adducts are appropriate descriptors for predicting the major product of the reactions at least in the cases study here. The maximum hardness principle and the minimun electropilicity principle are obeyed in these regiospecific Diels–Alder reactions. The stereoselectivity of the D-A reactions has also been studied.