Catalytic Silylation in Organic Synthesis

Catalytic silylation encompasses a suite of methodologies for the selective formation of carbon–silicon bonds under mild conditions. Organosilicon compounds are prized for their unique combination of chemical stability, adjustable lipophilicity and versatile reactivity, finding roles in pharmaceuticals, agrochemicals and advanced materials. Over the past decade, the field has witnessed a shift from stoichiometric to catalytic approaches, exploiting transition-metal complexes, main-group Lewis acids and organocatalysts to activate hydrosilanes or disilanes for regio- and enantioselective transformations. Key reaction manifolds include hydrosilylation of unsaturated bonds, direct dehydrogenative C–H silylation and radical-mediated photocatalytic processes. Contemporary research is refining catalyst design to enable stereocontrol at silicon, chemodivergent pathways and dual catalysis under visible light. These advances have broadened access to chiral silicon centres, multifunctional vinylsilanes and silacyclic architectures, underpinning the global significance of catalytic silylation as a platform for complex molecule construction and functional material discovery.

Research from Nature Portfolio

Recent developments have achieved enantioconvergent construction of stereogenic silicon centres via Lewis base-catalysed dynamic kinetic silyletherification. By combining racemic chlorosilanes and chiral lactates under mild conditions, a range of enantioenriched silylethers is now accessible on multi-gram scale, enabling downstream elaboration into diverse organosilicon analogues. Complementing this, an enantioselective intermolecular C–H silylation protocol employs a reactive rhodium hydride catalyst to convert simple arenes into acyclic stereogenic Si–H compounds with high enantioselectivity. This strategy hinges on substrate design that suppresses self-reaction of prochiral silanes, showcasing a streamlined route to chiral silicon building blocks. In a separate advance, nickel(0) catalysis has unlocked chemodivergent reactions of silacyclobutanes with internal alkynes. Ligand choice dictates whether benzosilacycles or allyl vinylsilanes form, and a chiral phosphine ligand further delivers enantioenriched allyl vinylsilanes. This low-cost, complementary system expands the toolbox for controlled assembly of silacyclic and open-chain silicon frameworks.

Catalytic Silylation in Organic Synthesis publication trend

The graph below shows the total number of articles in catalytic silylation 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, typically catalysed by transition metals.

Dehydrogenative C–H silylation: Direct formation of a C–Si bond by activation of a carbon–hydrogen bond with concurrent removal of hydrogen.

Photoredox catalysis: Use of visible-light absorbing catalysts to generate reactive radical species for bond formation via single-electron transfer.

Silicon-stereogenic centre: A silicon atom bearing four different substituents, creating a chiral centre analogous to stereogenic carbon.

References

1. Enantioconvergent construction of stereogenic silicon via Lewis base-catalyzed dynamic kinetic silyletherification of racemic chlorosilanes. Nature Communications (2023).
2. Rhodium hydride enabled enantioselective intermolecular C–H silylation to access acyclic stereogenic Si–H. Nature Communications (2022).
3. Nickel(0)-catalyzed divergent reactions of silacyclobutanes with internal alkynes. Nature Communications (2022).
4. Substitution, Elimination, and Integration of Methyl Groups in Terpenes Initiated by C–H Bond Functionalization. ACS Central Science (2024).
5. Organocatalytic Asymmetric Synthesis of Si-Stereogenic Silyl Ethers. Journal of the American Chemical Society (2022).
6. Consecutive β,β′‐Selective C(sp3)−H Silylation of Tertiary Amines with Dihydrosilanes Catalyzed by B(C6F5)3. Angewandte Chemie International Edition (2021).