Reduction of aryl halides by consecutive visible light-induced electron transfer processes

• Published in: Science (American Association for the Advancement of Science) Vol. 346; no. 6210; pp. 725 - 728
• Main Authors: Ghosh, Indrajit, Ghosh, Tamal, Bardagi, Javier I., König, Burkhard
• Format: Journal Article
• Language: English
• Published: United States American Association for the Advancement of Science 07.11.2014; The American Association for the Advancement of Science
• Subjects: absorption; Anions; Aromatic compounds; Carbon - chemistry; Catalysis; Chemical reactions; Chlorides; Chlorides - chemistry; Chlorides - radiation effects; Electron transfer; Electron transfer reactions; Electron Transport; Energy; Halides; Hydrogen - chemistry; Light; Oxidation-Reduction; oxygen; Photocatalysis; Photons; Photosynthesis; Radicals; Reduction
• ISSN: 0036-8075; 1095-9203; 1095-9203
• DOI: 10.1126/science.1258232

Biological photosynthesis uses the energy of several visible light photons for the challenging oxidation of water, whereas chemical photocatalysis typically involves only single-photon excitation. Perylene bisimide is reduced by visible light photoinduced electron transfer (PET) to its stable and colored radical anion. We report here that subsequent excitation of the radical anion accumulates sufficient energy for the reduction of stable aryl chlorides giving aryl radicals, which were trapped by hydrogen atom donors or used in carbon-carbon bond formation. This consecutive PET (conPET) overcomes the current energetic limitation of visible light photoredox catalysis and allows the photocatalytic conversion of less reactive chemical bonds in organic synthesis.