Solvent-Controlled Switchable Domino Reactions of MBH Carbonate: Synthesis of Benzothiophene Fused α‑Pyran, 2,3-Dihydrooxepine, and Oxatricyclodecene Derivatives

Solvent-controlled switchable domino reactions between 2-alkylidenebenzothiophene-3­(2H)-ones and Morita–Baylis–Hillamn (MBH) carbonate were developed. All domino reactions exhibited excellent regioselectivity, producing a broad spectrum of benzothiophene-fused α-pyran, 2,3-dihydrooxepine, and oxatricyclodecene derivatives. Furthermore, [4 + 2], [4 + 3], and related domino reactions from identical substrates can be controlled.