[3+3] Annulation of donor–acceptor cyclopropanes with mercaptoacetaldehyde: application to the synthesis of tetrasubstituted thiophenes

Abstract

A conceptually new method for synthesis of tetrasubstituted thiophenes in two steps from trans-2-aroyl-3-aryl-cyclopropane-1,1-dicarboxylates and 1,4-dithiane-2,5-diol has been developed. It involves AlCl₃-mediated [3+3] annulation of the cyclopropane-derived 1,3-zwitterionic intermediates with in situ generated mercaptoacetaldehyde, followed by DBU-induced rearrangement of the resulting tetrahydrothiopyranols. The target thiophenes are produced in 55–82% yields.