Catalyst-Controlled Diastereoselective Synthesis of Bridged [3.3.1] Bis(Indolyl)-Oxanes and Oxepanes via Desymmetrization of Bis(Indolyl)-Cyclohexadienones

A catalyst-controlled divergent synthesis of bridged [3.3.1] bis(indolyl)-oxanes and cis-[6.7] fused bis(indolyl) oxepanes via diastereoselective desymmetrization of bis(indolyl)-cyclohexadienones is presented for the first time. The reaction is highly atom- and step-economic, furnishing sp3-rich functionalized bis(indolyl) derivatives in good to excellent yields with wide substrate scope. The reaction proceeds through Friedel-Crafts alkylation followed by catalyst-controlled selective C-C bond formation/rearrangement. Gram scale synthesis and synthetic utility to generate bis(indolyl) alkaloid-like molecular diversity were also illustrated.