Secondary benzylation with benzyl alcohols catalyzed by a high-valent heterobimetallic Ir-Sn complex

A highly efficient secondary benzylation procedure has been demonstrated using a high-valent heterobimetallic complex [Ir-2(COD)(2)(SnCl3)(2)(Cl)(2)(mu-Cl)(2)] 1 as the catalyst in 1,2-dichloroethane to afford the corresponding benzylated products in moderate to excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also with oxygen (alcohol), nitrogen (amide and sulfonamide), and sulfur (thiol) nucleophiles. Mechanistic investigation showed the intermediacy of the ether in this reaction. An electrophilic mechanism is proposed from Hammett correlation.