Iron and Manganese Catalysts for the Selective Functionalization of Arene C(sp2)-H Bonds by Carbene Insertion

Abstract

The first examples of the direct functionalization of non-activated aryl sp2 C-H bonds with ethyl diazoacetate (N2CHCO2Et) catalyzed by Mn- or Fe-based complexes in a completely selective manner are reported, with no formation of the frequently observed cycloheptatriene derivatives through competing Buchner reaction. The best catalysts are FeII or MnII complexes bearing the tetradentate pytacn ligand (pytacn= 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane). When using alkylbenzenes, the alkylic C(sp3)-H bonds of the substituents remained unmodified, thus the reaction being also selective toward functionalization of sp2 C-H bonds. Exclusive catalysis: Iron- and-manganese-based catalysts selectively functionalize the C(sp2)-H bonds of benzene or alkylbenzenes through the formal insertion of the CHCO2Et group from N2CHCO2Et (see scheme). When using alkylbenzenes, the alkylic C(sp3)-H bonds of the substituents remain unmodified