Iron(III)‐Catalyzed Intramolecular Friedel–Crafts Alkylation of Electron‐Deficient Arenes with π‐Activated Alcohols

Abstract “Deficient” but “efficient”, the first example of a catalytic Friedel–Crafts alkylation of arenes, carrying electron‐withdrawing groups, with alcohols is reported. The optimized iron(III) chloride (97%) catalyzed allylation, benzylation and propargylation procedures open an access to a range of tetrahydronaphthalenes, tetrahydroisoquinolines and tetrahydrobenzo[d]azepines featuring tertiary benzylic stereocenters in excellent yields (up to 92%) and short reaction times.