Catalytic Transformations of Epoxides in Organic Synthesis

Epoxides, three-membered cyclic ethers, occupy a central role in modern synthetic chemistry by virtue of their ring strain and versatile reactivity. Catalytic methodologies have transformed epoxides into a wealth of value-added products, spanning alcohols, ketones, amines and heterocycles. Key strategies include ring-opening reactions under Lewis or Brønsted acid catalysis, enantioselective ring closures, rearrangements such as the Meinwald process, and tandem or cascade sequences that construct complex frameworks in a single operation. Transition-metal catalysts—rhodium, iridium, nickel and others—have enabled regio- and stereocontrol in nucleophilic opening, while organocatalysts and biocatalysts have driven enantioselective protocols under mild, sustainable conditions. Recent advances marry green-chemistry principles with flow-reactor technology and earth-abundant catalysts, fostering industrial applicability in pharmaceuticals, agrochemicals and polymer precursors. The growing emphasis on carbon-neutral feedstocks has also prompted innovative deoxygenation and carbon-carbon bond-forming routes from epoxide precursors, underscoring global demand for efficient, selective and environmentally benign transformations.

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Catalytic Transformations of Epoxides in Organic Synthesis publication trend

The graph below shows the total number of articles in catalytic transformations of epoxides in organic synthesis across all publications each year (not limited to Nature Index journals).

Technical terms

Epoxide: A three-membered cyclic ether with significant ring strain that undergoes ring-opening reactions to form functionalised compounds.

Meinwald rearrangement: A catalytic isomerisation of epoxides to carbonyl compounds, typically mediated by Lewis acids or transition-metal complexes.

Pincer complex: A tridentate ligand framework tightly bound to a central metal, providing high thermal stability and tunable reactivity in catalysis.

Lewis acid: An electron-pair acceptor that activates electrophilic substrates such as epoxides by increasing ring polarization.

Oxidative addition: A step in which a metal centre inserts into a substrate bond, often leading to metal-alkyl or metal-alkoxide intermediates in epoxide activation.

References

1. Selective rearrangement of terminal epoxides into methylketones catalysed by a nucleophilic rhodium–NHC–pincer complex. Chemical Communications (2015).
2. Deoxygenation of Epoxides with Carbon Monoxide. Chemistry - A European Journal (2020).
3. A novel acid-catalyzed rearrangement of 2-substituted-3-(2-nitrophenyl)oxiranes for the synthesis of di- and mono-oxalamides. RSC Advances (2016).