Indium(III)-Catalyzed Synthesis of Benzo[ b]furans by Intramolecular Hydroalkoxylation of ortho-Alkynylphenols: Scope and Mechanistic Insights.

Abstract

Indium(III) halides catalyze the hydroalkoxylation reaction of ortho-alkynylphenols to afford benzo[ b]furans in good yields. The reaction proceeds with 5- endo- dig regioselectivity with a variety of phenols functionalized at the arene and alkyne moieties in high yields using InI3 (5 mol %) in DCE. Experimental and computational studies support a mechanism based on the indium(III) π-Lewis acid activation of the alkyne followed by nucleophilic addition of the phenol and final protodemetalation to afford the corresponding benzo[ b]furan. DFT calculations suggest that dimer In2I6 is the catalytic species through a novel double coordination with the alkyne and the hydroxyl group.