An unprecedented Ga­(OTf)3-catalyzed, temperature-controlled regiodivergent alkylation of 2-substituted indoles with trifluoromethylated 3-indolylmethanols is described that provides structurally diverse unsymmetrical 3,3′- and 3,6′-bis­(indolyl)­methanes with a CF3-containing quaternary carbon center in good to excellent yields under mild conditions. In addition, this present protocol could be successfully extended to the synthesis of difluoromethylated 3,3′- and 3,6′-bis­(indolyl)­methanes with excellent efficiency.

A green and efficient regioselective dehydrative Friedel‐Crafts arylation of trifluorinated 3‐indolyl(2‐thiophenyl) methanols with 2‐substituted indoles, catalyzed by DBSA (dodecylbenzenesulfonic acid) in water is described. This simple and atom‐economical protocol features a unique regioselective 1,8‐addition, operational simplicity, mild conditions, excellent functional group compatibility, and environmental benignity.

A synthetic approach for the synthesis 2phosphoryl-3-monofluorovinylindoles via cascade regioselective dehydrative phosphorylation/stereoselective defluorination of difluoromethylated 3-indolylmethanols and H-phosphine oxides under catalyst-and additive-free conditions is described. The reaction could be scaled-up without the need for column chromatography purification.

An efficient synthetic method to prepare architecturally challenging spiro tetrahydro‐3H‐dicyclopenta[a,b]naphthalene derivatives from Au(I)‐catalyzed intramolecular sequential cycloisomerization of linear 1,3,9‐ene‐allene‐ynes is described. The proposed cycloisomerization pathway involves an initial gold‐catalyzed 1,3‐ene‐allene cycloisomerization, followed by a formal [4+2] cycloaddition to give fused spirocarbocyclic products containing a quaternary centre.