Sunlight-Driven Copper-Catalyst Activation Applied to Photolatent Click Chemistry

• Published in: Chemistry : a European journal Vol. 20; no. 41; pp. 13181 - 13187
• Main Authors: Beniazza, Rédouane, Lambert, Romain, Harmand, Lydie, Molton, Florian, Duboc, Carole, Denisov, Sergey, Jonusauskas, Gedeminas, McClenaghan, Nathan D., Lastécouères, Dominique, Vincent, Jean-Marc
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 06.10.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Subjects: benzophenone; Catalysis; Catalysts; Chemical Sciences; Chemistry; Chemistry, Multidisciplinary; click chemistry; Copper; copper catalysts; Cycloaddition; Daylight; Electron transfer; Illumination; Organic chemistry; photoactivation; Photochemistry; photoinduced electron transfer; Physical Sciences; Reduction; Science & Technology; Synthesis (chemistry); COMPLEXES; click chemistry; SENSITIZED PHOTO-REDUCTION; PHOTOINITIATOR; ALKYL-HALIDES; NUCLEOPHILES; CYCLOADDITION; photoactivation; ELECTRON-TRANSFER; CROSS-COUPLINGS; C-C; photoinduced electron transfer; GENERATION; benzophenone; copper catalysts
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201404056

The synthesis, full characterization, photoreduction properties, and catalytic activity for the copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction of a copper(II)–DMEDA (N,N′‐dimethylethylendiamine) complex is reported. Spectroscopic studies (UV/Vis, EPR) demonstrated that under daylight illumination highly effective copper(II) to copper(I) reduction occurs in this complex. These findings are in agreement with a high photoreduction quantum yield value of 0.22 in MeOH, and a value approaching unity as determined in THF. The reduction process, which can also be conducted by irradiation at 365 nm by using a standard TLC (thin layer chromatography) lamp, is ascribed to a highly efficient photoinduced electron transfer (PET) process mediated by the benzophenone photosensitizer present in the carboxylate counterion. Having deaerated the reaction mixture, the photogenerated copper(I) species proved to be highly active for the CuAAC reaction, demonstrated by reactions conducted with low catalyst loading (0.5 mol %) on a range of clickable protected and non‐protected mono‐ and disaccharides. Once initiated, the reaction can be stopped at any time on introducing air into the reaction medium. Deoxygenation followed by irradiation restores the activity, making the copper(II)–DMEDA complex a switchable catalyst of practical value. Sunlight‐mediated copper(II) to copper(I) reduction occurs with unprecedented efficiency in complex 1, with a photoreduction quantum yield approaching unity in THF. The photogenerated copper(I) species proved highly reactive for the copper‐catalyzed azide–alkyne cycloaddition reaction, with the preparative‐scale synthesis of unprotected disaccharide 2 conducted under daylight illumination (see scheme).