LAUSR

We report on the activation of chlorinated methanes by the heterogeneous catalysts aluminum chlorofluoride (ACF) and high‐surface aluminum fluoride (HS‐AlF3) under moderate conditions. For comparison, chlorinated toluenes and 1,2‐dichloroethane were also tested. The strong Lewis acids are able to promote the cleavage of C−Cl bonds in the presence of Et3SiH. The C−Cl bonds were converted into C−H bonds through hydrodechlorination reactions or, in the presence of benzene, into C−C bonds through Friedel–Crafts type reactions. The catalytic reactions show high conversions.