Synthesis of amides and lactams in supercritical carbon dioxide

The Journal of Organic Chemistry
Xiao Yin MakRick L Danheiser

Abstract

Supercritical carbon dioxide can be employed as an environmentally friendly alternative to conventional organic solvents for the synthesis of a variety of carboxylic amides. The addition of amines to ketenes generated in situ via the retro-ene reaction of alkynyl ethers provides amides in good yield, in many cases with ethylene or isobutylene as the only byproducts of the reaction. Reactions with ethoxy alkynes are performed at 120-130 degrees C, whereas tert-butoxy derivatives undergo the retro-ene reaction at 90 degrees C. With the exception of primary, unbranched amines, potential side reactions involving addition of the amines to carbon dioxide are not competitive with the desired C-N bond-forming reaction. The amide synthesis is applicable to the preparation of beta-hydroxy and beta-amino amide derivatives, as well as amides bearing isolated carbon-carbon double bonds. Preliminary experiments aimed at developing an intramolecular variant of this process to afford macrolactams suggest that the application of CO(2)/co-solvent mixtures may offer advantages for the synthesis of large-ring compounds.

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Citations

May 20, 2016·Accounts of Chemical Research·Thomas G Minehan
Jun 23, 2015·European Journal of Organic Chemistry·Cyril HenryRichard J Whitby
Oct 19, 2016·Organic & Biomolecular Chemistry·Vincent James Gray, Jonathan D Wilden
Jan 5, 2013·Chemical Communications : Chem Comm·Sameer S KulkarniRoman Manetsch
Apr 14, 2011·Organic Letters·Pei-Chen Chiang, Jeffrey W Bode
Sep 22, 2012·Organic Letters·Charlie VerrierJean-Francois Poisson
Apr 8, 2015·The Journal of Organic Chemistry·Tharwat Mohy El DineJérôme Blanchet
Sep 10, 2021·The Journal of Organic Chemistry·Danielle L McConnellMax M Majireck

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