After establishing the generality of the developed alkylation of heteroarenes using gaseous C2-4 alkanes, we turned our attention to the introduction of a methyl unit through the activation of methane, one of the most abundant carbon-based feedstocks. Despite the synthetic appeal of this C1 building block, the extraordinary inertness of the C(sp3)-H bonds (BDE = 105 kcal/mol) has strongly limited its use as a methylating agent in organic chemistry. Re-optimization of the reaction parameters revealed that 20 mol% of FeCl₂, in combination with acetonitrile-TFA (3:1) as the solvent system and a residence time of 30 minutes, was optimal for the formation of the desired methylated phenanthridine (30) (See Supporting Information). Using this set of conditions, a series of electron-neutral, electron-deficient, and halogenated quinolines were methylated in medicinal chemistry-relevant quantities (30-35).