Selective amidation by a photocatalyzed umpolung reaction

Abstract

Herein, a metal-catalyzed organic transformation merged with another organophotocatalyst has been developed under mild conditions for the production of α-ketoamides.

Photoinduced Cascade C–N/C═O Bond Formation from Bromodifluoroalkyl Reagents, Amines, and H2O via a Triple-Cleavage Process

“…Recently, the selective amidation of 1,3-ketoamide with amine under CuI catalysis to form unsymmetrical oxalamides has been developed. 10 For example, in 2020, Tikhonova's group 11 achieved thioamidation/cyclocondensation/hydrolysis of 2,2′-biphenyl diamines with 2chloroacetamides and water in one pot, but this protocol was suitable for only substituted aromatic amines (Scheme 1a). Despite these achievements, developing additional mild and environmental protocols for synthesizing unsymmetrical oxalamides is still in high demand.…”

“…However, these known methods still exhibited drawbacks, such as a low atom economy, harsh conditions, and a cumbersome operation. Recently, the selective amidation of 1,3-ketoamide with amine under CuI catalysis to form unsymmetrical oxalamides has been developed . For example, in 2020, Tikhonova’s group achieved thioamidation/cyclocondensation/hydrolysis of 2,2′-biphenyl diamines with 2-chloroacetamides and water in one pot, but this protocol was suitable for only substituted aromatic amines (Scheme a).…”

Sustainable Amidation Reactions – Recent Advances

“…A selective amidation by a photocatalytic umpolung reaction was reported by the Maiti group . The strategy relies on a Cu‐catalyzed highly selective COCH 2 ‐amidation in the presence of electrophilic C α =O bonds, that is synchronized by an eosin Y (EY)‐photocatalysis.…”

One-Pot Synthesis of α-Ketoamides from α-Keto Acids and Amines Using Ynamides as Coupling Reagents

“…In the past decade, extensive effort has been dedicated to the development of various methods for the synthesis of such scaffolds. Numerous routes to the synthesis of α-ketoamides are based on various starting materials such as terminal alkenes, terminal alkynes, ethylarenes, aryl ketones, aryl aldehydes, 2-oxoaldehydes, arylethanols, 2-oxo alcohols, α-oxocarboxylic acids, 1,3-diones, benzoylacetonitrile, β-ketonitriles, and aryl iodides . Nevertheless, the oxidants (e.g., TBHP) or transition-metal catalysts (e.g., Pd, Cu or Zn) ,,, involved in most of the aforementioned works seem to be necessary.…”