Functionalization of Primary Carbon−Hydrogen Bonds of Alkanes by Carbene Insertion with a Silver-Based Catalyst

The complexes [TpBr3Ag]2·CH3COCH3 (1) and TpBr3Ag(thf) (2) catalyze the insertion of the :CHCO2Et group from ethyl diazoacetate (EDA) into the saturated C−H bonds of several C5, C6, and C8 linear and branched alkanes. In addition to secondary and/or tertiary sites, the unprecedented insertion into the primary C−H bonds of the substrates studied has been observed with variable regioselectivity, toward the methyl groups, within the range of 40−60% for branched and nearly 25% for linear alkanes.