An unprecedented utilization of 2,3-dimethoxyindolines (DiMeOINs) as a latent electrophile in regioselective In-catalyzed aromatic substitutions has been reported.

We report herein the formal cine-substitution/hydrolysis of 3-azidoindole intermediates generated from 3-azido-2-methoxyindolines (AZINs). This protocol enables the introduction of both various carboxylic acid and alcohol into indolin-3-ones at the C2-position,...

We have developed 3-azido-2-methoxyindolines (AZINs) as user-friendly, bench-stable, thermally stable and reactive 3-azidoindole surrogates for the first time.

This work reports the novel reactivity of hemiaminal as a precursor for indole editing at the multi-site. The HFIPpromoted indole editing of indoline hemiaminals affords 2arylindoles through a ring-switch sequence. The key to success of this transformation is to use a cyclic hemiaminal as an α-amino aldehyde surrogate under transient tautomeric control. This transformation features mild reaction conditions and good yields with broad functional group tolerance. The utility of this transformation is presented through the one-pot protocol and the synthesis of isocryptolepine.

The regioselective synthesis of both 2-and 3-alkoxyindoles from a common intermediate, 2-alkoxy-3-bromoindolines (ROBIN), is described. The 2-alkoxyindoles are obtained by a base-promoted regioselective elimination of HBr from ROBIN, whereas the synthesis of 3-alkoxyindoles is achieved by a silvermediated alkoxylation followed by an acid-promoted elimination of alkoxide. This key elimination features the complete regioselectivity and no need for catalysts, that makes it have potential synthetic applications. Furthermore, this protocol is user friendly because ROBIN is able to be prepared from commercially available indoles and is a bench-stable easy-to-handle crystalline substrate, thus allowing the concise synthesis of a variety of both 2-and 3-alkoxyindoles.