Selective multiple magnesiations of the thieno[3,2-b]thiophene scaffold

A full functionalization of all four positions of the thieno[3,2‐b]thiophene scaffold was achieved. Starting from 2,5‐dichlorothieno[3,2‐b]thiophene, magnesiation of the 3‐ and 6‐position using tmpMgCl?LiCl furnishes, after trapping with various electrophiles, 3,6‐difunctionalized dichlorothieno[3,2‐b]thiophenes. Subsequent dechlorination and regioselective metalation or regioselective magnesium insertion into the C? Cl bond provides fully functionalized thieno[3,2‐b]thiophenes. Furthermore, new condensed heterocycles and small oligomers of these compounds with potential applications in material chemistry have been prepared.