Direct Clay‐Catalyzed Friedel‐Crafts Arylation and Chlorination of the Hydrocarbon Adamantane

Multiple chlorinations and arylations at the tertiary positions of adamantane are promoted by FeCl3‐doped K10 montmorillonite in CCl4 or in aromatic solvents. The process, remarkably easy to implement, can be tailored to selective formation of monosubstituted 1‐adamantyl derivatives or 1,3‐disubstituted adamantanes. The process achieves alkylation at the meta‐ and para‐positions of toluene leading to a purely statistical distribution and displays no substrate specificity in competition experiments between toluene and benzene.