Catalytic Hydrothiolation of Unsaturated Carbon–Carbon Bonds

Catalytic hydrothiolation refers to the addition of thiols (R–SH) across carbon–carbon double or triple bonds to yield organosulfur compounds such as vinyl and alkyl thioethers. This transformation is attractive for its atom economy, operational simplicity and direct access to sulphur-containing motifs of high value in pharmaceuticals, agrochemicals and advanced materials. Key challenges include control of regioselectivity (Markovnikov versus anti-Markovnikov addition), stereoselectivity (E/Z alkene geometry) and suppression of side-reactions such as disulfide formation. A variety of catalytic platforms have been developed, spanning transition-metal complexes (rhodium, iridium, gold), heterogeneous and glass-based materials, as well as photo- and electrochemical systems. Mechanistically, metal-catalysed pathways often proceed via thiolate activation followed by migratory insertion into a coordinated unsaturated substrate, whereas photochemical routes generate thiyl radicals that add to the π bond. Advances in ligand design, catalyst support architecture and reaction engineering have improved activity, selectivity and sustainability, opening routes to structurally diverse thioethers under mild, recyclable and base-free conditions.

Research from Nature Portfolio

No recent Nature Portfolio content available.

Catalytic Hydrothiolation of Unsaturated Carbon–Carbon Bonds publication trend

The graph below shows the total number of articles in catalytic hydrothiolation of unsaturated carbon–carbon bonds across all publications each year (not limited to Nature Index journals).

Technical terms

Hydrothiolation: Addition of a thiol across a carbon–carbon double or triple bond to form a thioether.

Thiol: An organosulfur compound containing an –SH (sulfhydryl) group.

Vinyl sulfide: A thioether in which the sulfur atom is bonded to an sp2 carbon of an alkene.

Regioselectivity: Preference for bond formation at one position over another on an unsaturated substrate (e.g. Markovnikov vs anti-Markovnikov).

Stereoselectivity: Control over the geometric configuration (E or Z) of an alkene product.

References

1. Iron-Borophosphate Glass-Catalyzed Regioselective Hydrothiolation of Alkynes under Green Conditions. Catalysts (2023).
2. Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes. Catalysis Science & Technology (2021).
3. Visible‐Light‐Driven Thiol‐yne Reaction: A Practical Synthesis of (1,2‐diarylvinyl)(aryl/alkyl)sulfides. ChemPhotoChem (2020).