An intermolecular radical cascade reaction between readily prepared o‐methylthio‐arylamines or o‐methylselanyl‐arylamines and alkynes for the preparation of valuable benzothiophenes or benzoselenophenes is reported. These transformations occur efficiently with complete regioselectivity and the products are obtained in moderate to good yields. The current protocol is successfully applied to the synthesis of the key intermediates of the drug raloxifene and an AT1 receptor antagonist.
