Gallium Bromide-Promoted Dearomative Indole Insertion in 3‑Indolylmethanols: Chemoselective and (<i>Z</i>/<i>E</i>)‑Selective Synthesis of 3,3′-Bisindole Derivatives

Gallium bromide (GaBr₃)-promoted dearomative indole insertion in 3-indolylmethanols has been established, which chemoselectively constructs a biologically important 3,3′-bisindole framework bearing an all-carbon quaternary center in high yields and excellent (<i>Z</i>)-selectivities (up to 99% yield, all >95:5 <i>Z</i>/<i>E</i>). The reaction pathway was suggested to include a tandem sequence of Michael addition/C–C bond cleavage/nucleophilic addition, wherein the strong acidity of GaBr₃ played a crucial role in the key step of C–C bond cleavage. This reaction not only provides a new strategy for dearomatization of indoles, but also represents a new reaction category for 3-indolylmethanols, which involves a rarely reported late-stage C–C bond cleavage of 3-indolylmethanol derivatives. In addition, this approach also offers an efficient method for the synthesis of biologically important 3,3′-bisindole derivatives