article · The Journal of Organic Chemistry
A chemical method has been established to activate the Beckmann rearrangement of ketoximes, enabling the production of amides and lactams. The method employs readily available and economical geminal dichloroimidazolidinediones at a substoichiometric loading of ten mole percent. The transformation operates through a validated self-propagating mechanism that drives the reaction efficiently. Across an evaluation of twenty-three diverse substrates, the protocol achieved high yields, predominantly between ninety and ninety-eight percent, within reaction times typically ranging from ten to thirty minutes. Successful transformations were demonstrated on complex molecules, including a precursor required for manufacturing the monomer of nylon-12 as well as a complex steroidal substrate conducted on a preparative scale. This approach highlights the capacity of structurally distinct organic promoters to drive catalytic transformations via self-propagating cycles.
Amides and lactams are fundamental building blocks in polymer manufacturing and pharmaceutical chemistry. Standard industrial synthesis methods often require harsh conditions or stoichiometric reagents. Demonstrating that an economical, readily available organic promoter can rapidly drive these transformations at low loadings offers a more efficient and potentially milder pathway for producing critical industrial compounds.
The method directly targets the synthesis of amides and lactams, which are vital for industrial polymer production, such as nylon-12, and specialty chemical synthesis. Chemical manufacturers and pharmaceutical development teams could utilise this efficient, rapid protocol. Because it operates on a preparative scale for complex molecules and yields high outputs in under thirty minutes, the technology represents applied laboratory research that provides a clear basis for further process development and scale-up testing.
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A novel protocol for the activation of the Beckmann rearrangement utilizing the readily available and economical geminal dichloroimidazolidinediones (DCIDs) on a substoichiometric scale (10 mol %) has been developed. A unique self-propagating mechanism for the substoichiometric dichloroimidazolidinedione-activated transformation was proposed and validated. The substrate scope of the developed protocol has been demonstrated by 23 examples with good to excellent yields (mostly 90-98%) in a short time (mostly 10-30 min), including a substrate for synthesizing the monomer of nylon-12 and a complicated steroidal substrate on a preparative scale. This research not only unveils for the first time the synthetic potential of substoichiometric amounts of dichloroimidazolidinediones in promoting chemical transformation but also offers yet another important illustration of the self-propagating cycle in the context of the Beckmann rearrangement activated by a structurally novel organic promoter.
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DOI: 10.1021/acs.joc.7b02983
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