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Ligand‐Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis

Chang‐Sheng Kuai, Ding‐Wei Ji, Chaoyang Zhao, Heng Liu, Yan‐Cheng Hu, Qing‐An Chen

2020Angewandte Chemie22 citationsDOIOpen Access PDF

Abstract

Abstract A method for the regiodivergent and stereoselective hydrosilylation of the basic industrial 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 ligand. Experimental studies and analysis were carried out to elucidate the reaction mechanism and the factors enabling manipulation of the regioselectivity. This study contributes to the art of regioselectivity control in alkene hydrofunctionalization.

Topics & Concepts

RegioselectivityHydrosilylationSilanesChemistryLigand (biochemistry)Allylic rearrangementAlkeneIsopreneOrganic chemistryImineCatalysisSilaneCopolymerBiochemistryPolymerReceptorOrganoboron and organosilicon chemistryAsymmetric Hydrogenation and CatalysisOrganometallic Complex Synthesis and Catalysis
Ligand‐Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis | Litcius