Effects of Molecular Oxygen, Solvent, and Light on Iridium-Photoredox/Nickel Dual-Catalyzed Cross-Coupling Reactions

J Org Chem. 2015 Aug 7;80(15):7642-51. doi: 10.1021/acs.joc.5b01193. Epub 2015 Jul 13.

Abstract

In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp(3)-sp(2) carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbon / chemistry*
  • Catalysis
  • Iridium / chemistry*
  • Light
  • Molecular Structure
  • Nickel / chemistry*
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Photochemical Processes
  • Reproducibility of Results
  • Solvents / chemistry

Substances

  • Solvents
  • Iridium
  • Carbon
  • Nickel
  • Oxygen