Nickel-Mediated Photoreductive Cross Coupling of Carboxylic Acid Derivatives for Ketone Synthesis

Chemistry. 2021 Dec 23;27(72):18168-18174. doi: 10.1002/chem.202103486. Epub 2021 Nov 23.

Abstract

A simple visible light photochemical, nickel-catalyzed synthesis of ketones from carboxylic acid-derived precursors is presented. Hantzsch ester (HE) functions as a cheap, green and strong photoreductant to facilitate radical generation and also engages in the Ni-catalytic cycle to restore the reactive species. With this dual role, HE allows for the coupling of a large variety of radicals (1°,2°, benzylic, α-oxy & α-amino) with aroyl and alkanoyl moieties, a new feature in reactions of this type. With both precursors deriving from abundant carboxylic acids, this protocol is a welcome addition to the organic chemistry toolbox. The reaction proceeds under mild conditions without the need for toxic metal reagents or bases and shows a wide scope, including pharmaceuticals and complex molecular architectures.

Keywords: carboxylic acids; ketones; nickel; photocatalysis; radicals.

MeSH terms

  • Carboxylic Acids
  • Catalysis
  • Ketones*
  • Nickel*
  • Oxidation-Reduction

Substances

  • Carboxylic Acids
  • Ketones
  • Nickel