Hydrosilylation Catalysis in Organic Synthesis

Hydrosilylation is the addition of a silicon–hydrogen bond across unsaturated carbon–carbon bonds to form organosilicon compounds, a transformation central to the manufacture of silicone materials, pharmaceuticals and fine chemicals. Traditional homogeneous catalysts have relied on noble metals, notably platinum, but recent years have witnessed a shift towards base-metal systems that offer cost, sustainability and unique reactivities. Mechanistic elucidation of catalytic cycles—encompassing oxidative addition of Si–H, alkene or alkyne insertion and reductive elimination—has been guided by spectroscopic, crystallographic and computational studies. Advances in ligand design now enable precise control over regioselectivity and stereoselectivity, while emerging radical and catalyst-free approaches expand substrate scope. The global significance of hydrosilylation lies in its versatility, mild conditions and compatibility with diverse functional groups, underpinning both industrial processes and cutting-edge asymmetric synthesis.

Research from Nature Portfolio

Recent studies have demonstrated ligand-controlled copper hydride catalysts for 1,2- and 1,4-hydrosilylation of 1,3-enynes, delivering enantiomerically enriched propargyl and allenylsilanes with up to 99 % ee under mild conditions. Mechanistic investigations implicate allenylcopper intermediates and selective four- or six-membered transition states driving both regio- and enantioselectivity. Seminal work in iron catalysis introduced 1,10-phenanthroline ligands that endow base-metal catalysts with benzylic and Markovnikov selectivity in alkene hydrosilylation, highlighting π–π interactions as key determinants. More recently, palladium catalysis with chiral phosphoramidite ligands has achieved stereospecific Si–C coupling in maleimide hydrosilylation, furnishing axially chiral succinimides with near-perfect diastereo- and enantioselectivity. These advances exemplify the synergy between ligand architecture and mechanistic precision, broadening the scope of asymmetric organosilicon synthesis.

Hydrosilylation Catalysis in Organic Synthesis publication trend

The graph below shows the total number of articles in hydrosilylation catalysis in organic synthesis across all publications each year (not limited to Nature Index journals).

Technical terms

Hydrosilylation: Addition of a silicon–hydrogen bond across an unsaturated carbon–carbon bond to form organosilicon compounds.

Regioselectivity: Preference for bond formation at one site over others in an unsymmetrical substrate, dictating the distribution of constitutional isomers.

Enantioselectivity: Preferential formation of one enantiomer over its mirror image in chiral product synthesis.

Ligand: A molecule bound to a metal centre that modulates the electronic and steric properties of a catalyst.

References

1. Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes. Nature Communications (2023).
2. Cobalt(I)‑Catalyzed Transformation of Si–H Bonds: H/D Exchange in Hydrosilanes and Hydrosilylation of Olefins. ACS Catalysis (2023).
3. Spin effect on redox acceleration and regioselectivity in Fe-catalyzed alkyne hydrosilylation. National Science Review (2023).
4. Ligands with 1,10-phenanthroline scaffold for highly regioselective iron-catalyzed alkene hydrosilylation. Nature Communications (2018).
5. Stereospecific Si-C coupling and remote control of axial chirality by enantioselective palladium-catalyzed hydrosilylation of maleimides. Nature Communications (2020).
6. Phenanthroline-imine ligands for iron-catalyzed alkene hydrosilylation. Chemical Science (2022).