Ligand Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis.

A regiodivergent and stereoselective hydrosilylation of basic industrial feedstock isoprene with unactivated silanes has been developed using earth-abundant iron catalyst. The manipulation of regioselectivity relies on fine modification of the coordination geometry of iron center. While a bidentate pyridine imine ligand promotes the formation of allylic silanes via a 4,1-addition, the selectivity toward 3,4-adduct homoallylic silanes was achieved by switching to tridentate nitrogen ligand. Experimental studies and analysis have been performed to interpret the mechanism and the regioselective manipulation. This work contributes to the art of regioselective control in alkene hydrofunctionalization.