Wednesday, April 22, 2020

BECKMANN REARRANGEMENT

Beckmann Rearrangement





An acid-induced rearrangement of oximes to give amides.
This reaction is related to the Hofmann and Schmidt Reactions and the Curtius Rearrangement, in that an electropositive nitrogen is formed that initiates an alkyl migration.



Mechanism of the Beckmann Rearrangement





Oximes generally have a high barrier to inversion, and accordingly this reaction is envisioned to proceed by protonation of the oxime hydroxyl, followed by migration of the alkyl substituent "trans" to nitrogen. The N-O bond is simultaneously cleaved with the expulsion of water, so that formation of a free nitrene is avoided.






Recent Literature




he Beckmann Rearrangement Executed by Visible-Light-Driven Generation of Vilsmeier-Haack Reagent




Dichloroimidazolidinedione-Activated Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams




Scope and Mechanism of a True Organocatalytic Beckmann Rearrangement with a Boronic Acid/Perfluoropinacol System under Ambient Conditions




Beckmann Rearrangement of Ketoximes to Lactams by Triphosphazene Catalyst




Efficient Iodine-Mediated Beckmann Rearrangement of Ketoximes to Amides under Mild Neutral Conditions




Beckmann Rearrangement of Oximes under Very Mild Conditions




Bromodimethylsulfonium Bromide-ZnCl2: A Mild and Efficient Catalytic System for Beckmann Rearrangement




Hypervalent Iodine-Mediated Beckmann Rearrangement of Ketoximes




Au/Ag-Cocatalyzed Aldoximes to Amides Rearrangement under Solvent- and Acid-Free Conditions




Beckmann reaction of oximes catalysed by chloral: mild and neutral procedures




Mercury-Catalyzed Rearrangement of Ketoximes into Amides and Lactams in Acetonitrile




Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions




Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage




Solvent-Free and One-Step Beckmann Rearrangement of Ketones and Aldehydes by Zinc Oxide

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