feedstock isoprene with unactivated silanes has been developed using earth‐abundant iron catalysts. The manipulation of regioselectivity relies on fine modification of the coordination geometry of the iron center. While a bidentate pyridine imine ligand promoted the formation of allylic silanes through 4,1‐addition, selectivity for the 3,4‐adduct homoallylic silanes was observed with a tridentate nitrogen