Decarbonylation Reactions in Organic Synthesis

Decarbonylation reactions involve the selective removal of a carbon monoxide (CO) fragment from an organic substrate. Typically mediated by transition-metal catalysts, these processes have evolved into versatile tools for the construction and modification of carbon-based frameworks. Mechanistically, decarbonylation proceeds via oxidative addition of an acyl precursor to the metal centre, followed by CO extrusion and subsequent reductive elimination to furnish the desired C–C or C–X bond. Classical substrates include aldehydes, acid chlorides, esters and formamides, but recent advances have broadened the scope to encompass aliphatic, heteroaromatic and polyfunctional systems. A diverse array of catalysts—ranging from palladium, nickel and rhodium to base-mediated metal-free protocols—has been developed to achieve high selectivity under mild conditions. The global significance of decarbonylation lies in its capacity to transform abundant feedstocks into value-added compounds, minimise stoichiometric waste and offer alternatives to hazardous carbon-monoxide gas through in situ CO generation or surrogate reagents. Applications span late-stage functionalisation in pharmaceutical synthesis, polymer modification and isotope labelling, underscoring the reaction’s impact on both academic inquiry and industrial practice.

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Decarbonylation Reactions in Organic Synthesis publication trend

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Technical terms

Decarbonylation: A reaction that removes a carbonyl (CO) unit from an organic molecule, often via transition-metal catalysis.

Oxidative addition: A step in which a metal centre inserts into a substrate’s bond, increasing its oxidation state by two units.

Reductive elimination: The converse of oxidative addition, where two ligands on a metal combine to form a new bond and the metal is reduced.

Acyl complex: A metal-bound intermediate in which the metal centre is coordinated to a carbonyl-derived acyl group.

Protodeformylation: A subtype of decarbonylation in which a formyl group is removed and replaced by a proton, yielding a C–H bond.

Global electrophilicity: A descriptor of a molecule’s tendency to accept electrons, used to assess reactivity in theoretical studies.

References

1. Theoretical Study of the Chemical Properties and the Reaction Pathway of Decarbonylative Alkylative Esterification of Styrenes with Aliphatic Aldehydes. Journal of Chemistry (2022).
2. Palladium on carbon in PEG-400/Cyclohexane: Recoverable and recyclable catalytic system for efficient decarbonylation of aldehydes. Journal of the Serbian Chemical Society (2022).
3. tert -Butoxide-Mediated Protodeformylative Decarbonylation of α-Quaternary Homobenzaldehydes. SynOpen (2024).