Catalytic Transformations in Organic Synthesis of Propargylic Alcohols

Catalytic transformations of propargylic alcohols represent a pivotal area of contemporary organic synthesis, enabling the efficient construction of complex molecular architectures. Propargylic alcohols, characterised by an alkyne adjacent to a hydroxyl group, serve as versatile building blocks in the formation of enones, esters, furans and heterocycles. Transition-metal catalysts—particularly gold, ruthenium, copper, iron and nickel—facilitate a spectrum of pathways including rearrangements, additions, cyclisations and hydration reactions under mild conditions with high chemo- and regioselectivity. Acid-catalysed rearrangements, such as the Meyer–Schuster reaction, convert propargylic alcohols into α,β-unsaturated carbonyl compounds, furnishing key intermediates for natural product synthesis. Anti-Markovnikov addition strategies exploit metal-alkyne complexes to deliver carboxylic acids or nucleophiles across the triple bond, while hydration and dihalohydration processes generate β-hydroxy ketones and halogenated motifs for subsequent elaboration. Recent developments in chiral ligand design and mechanistic elucidation have driven progress towards enantioselective variants, enhancing the utility of propargylic alcohols in pharmaceutical and agrochemical targets. Optimisation of catalyst stability and turnover, together with cascade and tandem sequences, has elevated atom economy and sustainability, underscoring the global significance of these transformations in green chemistry and industrial applications.

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Catalytic Transformations in Organic Synthesis of Propargylic Alcohols publication trend

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Technical terms

Propargylic alcohol: An alcohol in which the hydroxyl-bearing carbon is adjacent to a carbon–carbon triple bond.

Meyer–Schuster rearrangement: An acid-catalysed conversion of propargylic alcohols into α,β-unsaturated carbonyl compounds via enyne intermediates.

Anti-Markovnikov addition: An addition reaction in which the incoming group attaches to the less substituted carbon of an unsaturated bond, contrary to Markovnikov’s rule.

Turnover number (TON): The number of substrate molecules converted per catalyst molecule before deactivation.

Protodemetallation: The proton-mediated cleavage of a metal–carbon bond to liberate the organic product and regenerate the catalyst.

References

1. Catalyst speciation and deactivation in the ruthenium-mediated transformation of ethynyl-β-ionol to α,β-unsaturated esters for vitamin A synthesis. Catalysis Science & Technology (2025).
2. Intercepting the Gold‐Catalysed Meyer–Schuster Rearrangement by Controlled Protodemetallation: A Regioselective Hydration of Propargylic Alcohols. Advanced Synthesis & Catalysis (2016).
3. Dihalohydration of Alkynols: A Versatile Approach to Diverse Halogenated Molecules. European Journal of Organic Chemistry (2018).
4. Meyer–Schuster rearrangement of propargylic alcohols mediated by phosphorus-containing Brønsted acid catalysts. Organic & Biomolecular Chemistry (2022).