Catalytic Asymmetric Functionalization of Alkenes

Alkenes are fundamental building blocks in organic synthesis, valued for their propensity to undergo regio- and stereoselective addition reactions. Catalytic asymmetric functionalization of alkenes harnesses chiral catalysts—often transition-metal complexes or organocatalysts—to introduce two new substituents across the carbon–carbon double bond with precise control over absolute configuration. Classic hydrofunctionalizations, such as hydroboration and hydroamination, have matured into highly enantioselective protocols. More recent advances employ dual‐catalysis strategies or photoredox activation to achieve complex difunctionalizations, including oxyamination, aminochlorination and alkoxy-sulfenylation. Mechanistic insights into substrate coordination, migratory insertion and enantiodiscriminating transition states have underpinned catalyst design, leading to improved activity with unactivated alkenes and enhanced tolerance of polar functional groups. These developments have found applications in the synthesis of chiral pharmaceuticals, agrochemicals and natural products, enabling streamlined access to motifs such as β-amino alcohols, vicinal diamines and heterocycle-fused scaffolds. The global significance of this field is reflected in its contribution to more sustainable processes, employing lower catalyst loadings and benign reagents to reduce waste and energy consumption.

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Catalytic Asymmetric Functionalization of Alkenes publication trend

The graph below shows the total number of articles in catalytic asymmetric functionalization of alkenes across all publications each year (not limited to Nature Index journals).

Technical terms

Alkene: Hydrocarbon containing at least one carbon–carbon double bond.

Enantioselectivity: Preference for formation of one enantiomer over the other in a chiral reaction.

Chiral catalyst: Catalyst bearing a stereogenic element that induces asymmetry in the product.

1,2-Alkoxy-sulfenylation: Simultaneous addition of alkoxy and thio groups across an alkene.

Aminothiolation: Concomitant addition of amine and thiol functionalities to an unsaturated bond.

Bunte salt: Sodium thiosulfate derivative acting as a masked thiol donor under oxidative conditions.

References

1. Sulfenofunctionalization of Chiral α‐Trifluoromethyl Allylboronic Acids: Asymmetric Synthesis of SCF3, SCF2R, SCN and SAr Compounds. Angewandte Chemie International Edition (2022).
2. Aminothiolation of alkenes with azoles and Bunte salts. Frontiers in Chemistry (2024).
3. Asymmetric Radical-Type 1,2-Alkoxy-Sulfenylation of Benzoxazole-2-Thiols to Vinylarenes Catalyzed by Chiral Vanadyl Complexes. ACS Catalysis (2024).