Heterogeneous Catalytic Hydroarylation of Olefins at a Nanoscopic Aluminum Chlorofluoride

Abstract

AbstractWe report on hydroarylation reactions of arenes with olefins under very mild conditions catalyzed heterogeneously by aluminum chlorofluoride (ACF; AlClxF3−x, x≈0.05–0.25). The reactions of benzene and toluene with ethylene or propylene proceed with high conversions to afford various alkylated arenes. For cyclohexene and 1‐hexene, the reactions require higher temperatures and the conversions are lower. ACF also catalyzes the hydroarylation of 1,3,5‐trifluorobenzene and pentafluorobenzene with ethylene and propylene. The alkylations of arenes with non‐fluorinated olefins resemble typical Friedel–Crafts chemistry to give rise to Markovnikov regioselectivity. The reaction of CF3CH=CH2 with benzene proceeds with anti‐Markovnikov regioselectivity to give the fluorinated olefin PhCHCH=CF2 and the alkylation product PhCH2CH2CF3 as products of C−F and C−H activation.