Organoselenium Catalysis in Organic Synthesis

Organoselenium catalysis has developed into a versatile platform for enabling selective transformations in organic chemistry. The unique redox properties of selenium, lying between those of sulphur and tellurium, allow organoselenium reagents to mediate both oxidative and reductive pathways under mild conditions. Such catalysts can promote electrophilic additions to alkenes, para-selective functionalisations of aromatic rings, atom-transfer processes and asymmetric oxidations. Biomimetic inspiration from glutathione peroxidase has guided the design of selenium-based catalysts that emulate enzymatic peroxide decomposition, while catalytic cycles exploiting in situ generation of active selenium species offer enhanced sustainability. The field has witnessed rapid expansion into enantioselective synthesis, green oxidation protocols using hydrogen peroxide and air as terminal oxidants, and applications to complex molecule construction. Organoselenium catalysis now underpins key steps in pharmaceutical syntheses, agrochemical production and materials science, reflecting its broad practical impact and growing industrial relevance.

Research from Nature Portfolio

Recent studies have extended the scope of selenium catalysis into aromatic amination. A catalytic para-amination of phenols has been demonstrated using a phenylselenyl bromide precursor, converting N-aryloxyacetamides into N-acetyl p-aminophenols under mild conditions. Experimental and computational analyses reveal that a labile selenium–nitrogen bond facilitates turnover of the catalytic cycle. The method tolerates para-substitution and permits dearomatising cyclodienone formation from tyrosine derivatives. This advance not only broadens the repertoire of selenium-mediated aromatic functionalisation but also showcases bioinspired redox control for constructing value-added motifs in a fluorogenic buffer system.

Organoselenium Catalysis in Organic Synthesis publication trend

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

Technical terms

Organoselenium catalysis: Use of carbon-bound selenium compounds to accelerate chemical reactions by providing unique redox or electrophilic activation pathways.

Electrophilic selenium catalysis: Catalytic cycle in which selenium species act as electrophiles to activate unsaturated substrates for addition or cyclisation.

Redox functional group interconversion: Transformation of one functional group to another via controlled oxidation or reduction steps, often mediated by selenium catalysts.

Selenium-π-acid catalyst: Chiral selenium compound that coordinates to π-systems (e.g. alkenes) to promote enantioselective oxidative functionalisation.

References

1. Recent Advances in Selenium‐Mediated Redox Functional Group Interconversions. The Chemical Record (2024).
2. A selenium-catalysed para-amination of phenols. Nature Communications (2018).
3. Rational Design of Chiral Selenium-π-Acid Catalysts. Catalysts (2019).
4. Developments in Synthetic Application of Selenium(IV) Oxide and Organoselenium Compounds as Oxygen Donors and Oxygen-Transfer Agents. Molecules (2015).
5. Continuous Bioinspired Oxidation of Sulfides. Molecules (2020).