Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes

• Published in: Science (American Association for the Advancement of Science) Vol. 365; no. 6451; pp. 360 - 366
• Main Authors: Ghosh, Indrajit, Khamrai, Jagadish, Savateev, Aleksandr, Shlapakov, Nikita, Antonietti, Markus, König, Burkhard
• Format: Journal Article
• Language: English
• Published: United States American Association for the Advancement of Science 26.07.2019; The American Association for the Advancement of Science
• Subjects: Aromatic compounds; Carbon; Carbon nitride; Catalysis; Catalysts; Centrifugation; Chromophores; Cyanides; Electrons; Holes (electron deficiencies); Intermediates; Nucleophiles; Oxidation; Photoredox catalysis; Redox reactions; Semiconductor materials; Substrates
• ISSN: 0036-8075; 1095-9203; 1095-9203
• DOI: 10.1126/science.aaw3254

Photoexcited electron-hole pairs on a semiconductor surface can engage in redox reactions with two different substrates. Similar to conventional electrosynthesis, the primary redox intermediates afford only separate oxidized and reduced products or, more rarely, combine to one addition product. Here, we report that a stable organic semiconductor material, mesoporous graphitic carbon nitride (mpg-CN), can act as a visible-light photoredox catalyst to orchestrate oxidative and reductive interfacial electron transfers to two different substrates in a two- or three-component system for direct twofold carbon–hydrogen functionalization of arenes and heteroarenes. The mpg-CN catalyst tolerates reactive radicals and strong nucleophiles, is straightforwardly recoverable by simple centrifugation of reaction mixtures, and is reusable for at least four catalytic transformations with conserved activity.