Catalyst-controlled switchable [4 + 1], [4 + 3] and [3 + 2] domino reactions of azadienes and MBH carbonates: diverse synthesis of benzothiophene fused derivatives

Abstract

Catalyst-controlled switchable domino reactions between azadienes bearing a benzothiophene moiety and isatin-derived MBH carbonates were developed. The [4 + 1] annulation was triggered in the presence of DABCO, giving a variety of benzothiophene fused pyrrole derivatives, while the [4 + 3] annulation occurred when changing the catalyst to DMAP. Furthermore, the [3 + 2] annulation mode was observed with the use of catalytic Ph₂PMe. Additionally, the synthetic utility of these domino reactions was demonstrated by gram-scale experiments and simple transformations of the products. To the best of our knowledge, catalyst-controlled synthesis of benzothiophene fused or spiro derivatives has rarely been reported.