Base-Promoted C–O Bond Cleavage of Primary Alcohols by Iridium(III) Porphyrin Chloride

Abstract

Various Ir­(por)-benzyls and Ir­(por)-alkyls (por = porphyrinato dianion ligand) were successfully synthesized with benzyl and 1° alkyl alcohols by C–O bond cleavage with Ir­(ttp)­(CO)Cl (ttp = 5,10,15,20-tetraphenylporphyrinato dianion) in alkaline media. The alkylation products were afforded in up to 92% yields. Mechanistic investigations suggest that both the Ir­(ttp)− anion and Ir­(ttp)H are key intermediates via a hydrogen-borrowing pathway.