Catalytic Reactions Involving Allylic Alcohols

Allylic alcohols serve as versatile building blocks in contemporary catalysis, enabling the formation of carbon–carbon and carbon–heteroatom bonds with high atom economy. Unlike traditional approaches that require pre-activated derivatives, direct activation of the hydroxyl moiety under transition-metal catalysis circumvents wasteful steps and minimises by-products. Key activation modes involve formation of π-allyl metal intermediates in palladium- or nickel-catalysed processes, cooperative hydrogen-bonding arrays to facilitate oxidative addition, and multifunctional surface-supported catalysts that combine nanoparticle hydrogenation with molecular coupling. Recent efforts have emphasised sustainable methodologies, including solvent-free mechanochemistry and one-pot tandem procedures, achieving exceptional functional-group tolerance, low catalyst loadings and operational simplicity. These advances are reshaping pathways to pharmaceutically relevant allylated compounds, natural product frameworks and fine chemicals by exploiting readily available allylic alcohols under mild, environmentally benign conditions.

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Catalytic Reactions Involving Allylic Alcohols publication trend

The graph below shows the total number of articles in catalytic reactions involving allylic alcohols across all publications each year (not limited to Nature Index journals).

Technical terms

Allylic alcohol: An alcohol in which the hydroxyl group is adjacent to a carbon–carbon double bond, acting as a latent electrophile in catalysed allylation.

Tsuji–Trost reaction: A palladium-catalysed allylic substitution in which a π-allyl palladium complex undergoes nucleophilic attack to form new C–C or C–heteroatom bonds.

N-heterocyclic carbene (NHC): A strong σ-donating ligand that stabilises metal centres and enhances catalyst activity and selectivity in organometallic transformations.

Atom economy: A metric reflecting the proportion of reactant atoms incorporated into the desired product, promoting resource-efficient synthesis.

Mechanochemistry: The initiation of chemical transformations by mechanical forces, such as grinding or milling, often enabling solvent-free reactions.

π-allyl intermediate: A transient species formed when an allylic substrate coordinates to a metal centre, facilitating regioselective nucleophilic attack at the allyl termini.

References

1. Allylation of C‐, N‐, and O‐Nucleophiles via a Mechanochemically‐Driven Tsuji–Trost Reaction Suitable for Late‐Stage Modification of Bioactive Molecules. Angewandte Chemie International Edition (2023).
2. One-Pot Multicomponent Synthesis of Allyl and Alkylamines Using a Catalytic System Composed of Ruthenium Nanoparticles on Copper N‑Heterocyclic Carbene-Modified Silica. ACS Catalysis (2022).
3. C−C Bond Formation by Dual Pyrrolidine and Nickel Catalysis: Allylation of Ketones by Allylic Alcohols. Advanced Synthesis & Catalysis (2024).