Desulfurization and Oxidation of Thiocarbonyl Compounds

Thiocarbonyl compounds, characterised by a carbon–sulfur double bond (C=S), occupy a pivotal role in both synthetic chemistry and industrial processes. Their reactivity diverges markedly from that of conventional carbonyls owing to the larger atomic radius and lower electronegativity of sulfur, which influences bond strength, polarisation and orbital overlap. Desulfurization of these motifs—removal of the sulphur atom to regenerate a carbonyl centre—underpins applications ranging from fine‐chemical synthesis to the upgrading of fossil fuels through hydrodesulfurization. Concurrently, controlled oxidation of thiocarbonyls enables the formation of valuable sulphoxide and sulfone derivatives, which find utility in medicinal chemistry, materials science and agrochemicals. Recent advances have focused on selective catalysts, green oxidants and photochemical strategies to achieve high yields under mild conditions, thereby reducing waste and energy consumption. The global significance of these transformations is underscored by stringent environmental regulations on sulphur emissions and the ever‐growing demand for sustainable synthetic methodologies.

Research from Nature Portfolio

Recent studies have demonstrated a bimetallic palladium–lanthanide complex that mediates desulfurization of thioureas at ambient temperature, allowing direct access to ureas in high selectivity. Another contribution utilises a visible‐light photoredox system in combination with a cobalt cocatalyst to achieve oxidative desulfurization of thioketones, affording diketones under entirely metal‐free conditions. A third investigation reports a tailored metal–organic framework with embedded cerium centres for tandem desulfurization–oxidation, converting thioesters into esters and sulfone by‐products with minimal over‐oxidation.

Desulfurization and Oxidation of Thiocarbonyl Compounds publication trend

The graph below shows the total number of articles in desulfurization and oxidation of thiocarbonyl compounds across all publications each year (not limited to Nature Index journals).

Technical terms

Thiocarbonyl compound: A molecule containing a C=S double bond, analogous to a carbonyl (C=O) but with distinct reactivity due to the sulphur atom.

Desulfurization: A chemical transformation in which a sulphur atom is removed from an organic substrate, often converting a C=S bond into a C=O bond.

Oxidation: A redox process whereby the oxidation state of sulphur in a thiocarbonyl is increased, producing sulfoxides (S+2) or sulfones (S+4).

Hydrodesulfurization (HDS): An industrial process using hydrogen and catalysts to remove sulfur from petroleum fractions, converting thiocarbonyls and thiols to hydrocarbons and hydrogen sulfide.

Photoredox catalysis: A method utilising light-activated catalysts to promote single‐electron transfer events, enabling mild oxidation or reduction of substrates.