Heterogeneous Catalytic Hydroarylation of Olefins at a Nanoscopic Aluminum Chlorofluoride

摘要

We report on hydroarylation reactions of arenes with olefins under very mild conditions catalyzed heterogeneously by aluminum chlorofluoride (ACF; AlClxF3-x, x approximate to 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 pentafluoro-benzene 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.