Beckmann Rearrangement Catalysis in Organic Synthesis
Summary
The Beckmann rearrangement is a cornerstone transformation in organic chemistry, converting ketoximes into amides or cyclic lactams via acid-catalysed migration of an alkyl or aryl substituent. First discovered in the late 19th century, it underpins the industrial synthesis of caprolactam for nylon and numerous fine chemicals. Traditional protocols employ harsh reagents such as oleum or concentrated sulphuric acid, necessitating large acid loads and generating corrosive waste. Modern efforts focus on milder, catalytic systems that enhance selectivity, reduce environmental impact and improve atom economy. Advances include the use of Brønsted and Lewis acids in substoichiometric amounts, heterogenous solid acids supported on inorganic matrices, protic and task-specific ionic liquids, and metal-based catalysts that operate under ambient or near-ambient conditions. Recent mechanistic studies reveal that activation of the oxime to a nitrilium ion intermediate governs migration aptitude and product distribution, while interrupted rearrangements via novel activated intermediates open new pathways to amide derivatives. Continuous-flow and supported-catalyst formats further address scalability and catalyst reuse. These innovations broaden the scope of Beckmann rearrangement catalysis, enabling efficient access to diverse amide architectures and cyclic lactams with diminished waste and energy requirements, and underscore its enduring relevance in pharmaceutical, agrochemical and materials contexts.
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Beckmann Rearrangement Catalysis in Organic Synthesis publication trend
The graph below shows the total number of articles in beckmann rearrangement catalysis in organic synthesis across all publications each year (not limited to Nature Index journals).
Technical terms
Ketoxime: an oxime derived from a ketone, featuring the functional group C=NOH.
Beckmann rearrangement: the acid-catalysed conversion of ketoximes into amides or lactams via migration of an adjacent substituent.
Amide: an organic functional group consisting of a carbonyl bonded to a nitrogen atom.
Lactam: a cyclic amide formed by intramolecular Beckmann rearrangement of cyclic ketoximes.
Brønsted acid: a proton donor that activates the oxime for rearrangement.
Lewis acid: an electron-pair acceptor used to polarise the C=NOH bond and facilitate migration.
Ionic liquid: a salt that is liquid at ambient temperature, serving as both solvent and catalyst in rearrangement reactions.
Atom economy: a metric of how efficiently reactant atoms are incorporated into the desired product.
References
- A General Method to Access Underexplored Ylideneamino Sulfates as Interrupted Beckmann-Type Rearrangement Intermediates. Molecules (2024).
- Beckmann Rearrangement with Improved Atom Economy, Catalyzed by Inexpensive, Reusable, Bro̷nsted Acidic Ionic Liquid. ACS Sustainable Chemistry & Engineering (2022).
- Silica Gel Supported Chlorosulfonic Acid Catalyzed Beckmann Rearrangement of Cyclohexanone Oxime in Liquid Phase. Journal of Physics Conference Series (2024).
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