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

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journal contribution
posted on 2016-10-28, 00:00 authored by Cong-Shuai Wang, Tao Fan, Hong-Hao Zhang, Can Li, Yang Shen, Guang-Jian Mei, Feng Shi
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 (Z)-selectivities (up to 99% yield, all >95:5 Z/E). 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.