Nickel(0)/NaHMDS adduct-mediated intramolecular alkylation of unactivated arenes via a homolytic aromatic substitution mechanism.

A variety of polycycles can be synthesized via an intramolecular alkylation cyclization promoted by Ni(PPh(3))(4) and NaHMDS. Mechanistic investigations support the catalytic nature of Ni(0) in the course of TEMPO scavenging experiments and its association with the substrate and NaHMDS to form an adduct by DOSY NMR.