Acid-Promoted Reaction of Trifluoromethylated Allyl Alcohols with Arenes. Stereoselective Synthesis of CF3‑Alkenes and CF3‑Indanes

Abstract

Reaction of 4-aryl-1,1,1-trifluorobut-3-en-2-ols with arenes under activation with anhydrous FeCl3 or FSO3H was studied. We found that the transformation led to trifluoromethylated alkenes or 1-trifluoromethylated indanes (CF3-indanes). The formation of these two types of reaction products strongly depends on the nucleophilicity of the starting arene and the electrophilicity of cationic intermediates generated from CF3-allyl alcohols under reaction conditions. Benzene, anisole, veratrole, and ortho-xylene lead exclusively to CF3-alkenes with an E-configuration. More π-donating polymethylated arenes (pseudocumene, mesitylene) afford only CF3-indanes with a predominantly cis-orientation of substituents at positions 1 and 3 of the indane ring. Meta- and para-xylenes show an intermediate behavior; they may form both CF3-alkenes and/or CF3-indanes. The mechanisms of the investigated transformations are discussed.