100609-02-7Relevant academic research and scientific papers
Catalytic Alkene Carboaminations Enabled by Oxidative Proton-Coupled Electron Transfer
Choi, Gilbert J.,Knowles, Robert R.
, p. 9226 - 9229 (2015)
Here we describe a dual catalyst system comprised of an iridium photocatalyst and weak phosphate base that is capable of both selectively homolyzing the N-H bonds of N-arylamides (bond dissociation free energies ～ 100 kcal/mol) via concerted proton-couple
Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer
Miller, David C.,Choi, Gilbert J.,Orbe, Hudson S.,Knowles, Robert R.
supporting information, p. 13492 - 13495 (2015/11/09)
Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.
