Typical Friedel-Crafts alkylation proceeds by the attack of a highly electrophilic carbocation towards the most nucleophilic site of an aromatic ring. In contrast, our 'anti-Friedel-Crafts' selectivity relies upon a nucleophilic alkyl radical attacking the most electrophilic site of an aromatic ring. 1,2 Thus, regioselectivity is largely governed by the ability of each carbon site in the aromatic system to accommodate an additional radical electron, with steric effects also playing a role.