Exhaustive Catalytic ortho-Alkoxylation of Azobenzenes: Flexible Access to Functionally Diverse Yellow-Light-Responsive Photoswitches

Müller-Deku, Adrian und Thorn-Seshold, Oliver (2022): Exhaustive Catalytic ortho-Alkoxylation of Azobenzenes: Flexible Access to Functionally Diverse Yellow-Light-Responsive Photoswitches. In: Journal of Organic Chemistry, Vol. 87, No. 24: pp. 16526-16531

Abstract

We develop the first method for catalytic, exhaustive ortho-alkoxylation of azobenzene photoswitches. Alkoxylation is known to improve the photoswitch properties that control azobenzenes' success in chemical biology or materials sciences, e.g., better completeness of both E-* Z and Z-* E photoisomerizations and >100 nm red shift of photoresponse. Our method enables straightforward late-stage diversification of photoswitches with interesting functional handles. We showcase four applications: using it to rationally tune lipophilicity, prepare isotopic tracers for metabolism studies, install full water solubility without ionic charges, and efficiently access previously difficult mixed-substituent photo switches. We also identified a previously unexplored mixedsubstituent tetra-ortho family, difluoro-dialkoxy-azobenzenes, whose photoresponse can outperform previous 'gold standard' tetrafluoro-, dichloro-difluoro-, and tetrachloro-azobenzenes in significant ways. We thus expect that both the scaffolds we showcase and the method we develop will impact broadly on photochemistry and photopharmacology.

• Item Type: Journal article
• Faculties: Chemistry and Pharmacy > Department of Pharmacy
• Subjects: 500 Science > 540 Chemistry
• ISSN: 0022-3263
• Language: English
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 201269156
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 239283807
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 400324123
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 426018126