Synergistic‐Catalysis‐Enabled Reaction of 2‐Indolymethanols with Oxonium Ylides for the Construction of 3‐Indolyl‐3‐Alkoxy Oxindole Frameworks

A synergistic‐catalysis‐enabled reaction of 2‐indolymethanols with oxonium ylides has been established that makes use of a three‐component reaction between 3‐diazooxindoles, alcohols, and 2‐indolymethanols under the cooperative catalysis of a metal complex and a Brønsted acid. This reaction has not only provided a new approach for the construction of 3‐indolyl‐3‐alkoxy oxindole scaffolds by utilizing the C3‐electrophilicity of an indole, but it is also the first example of a nucleophilic addition of a metal‐associated ylide to 2‐indolylmethanols. In addition, this reaction also includes a rarely reported trapping of onium ylides with aryl electrophiles. Mergers and acquisitions: A synergistic‐catalysis‐enabled reaction of 2‐indolymethanols with oxonium ylides affords 3‐indolyl‐3‐alkoxy oxindole frameworks through a three‐component reaction of 3‐diazooxindoles, alcohols, and 2‐indolymethanols.