Photoelectrochemical Iron(III) Catalysis for Late‐Stage C─H Fluoroalkylations
Vladimir Motornov, Sven Trienes, Simonetta Resta, João C. A. Oliveira, Zhipeng Lin, Zhi Liu, Tristan von Münchow, Claudia Stückl, Lutz Ackermann
Abstract
Chemo- and site-selective functionalization of complex molecules poses a fundamental challenge. Herein, we introduce a resource-economic photoelectrocatalysis strategy to enable versatile direct fluoroalkylations catalyzed by Earth-abundant iron and paired with the hydrogen evolution reaction (HER). Notably, the devised approach proved amenable to versatile late-stage C─H fluoroalkylations of bio-relevant heterocycles, such as xanthines, nucleobases, and nucleosides. Mechanistic studies supported a ligand-to-metal charge transfer-induced formation of the fluoroalkyl radical.
Topics & Concepts
PhotoexcitationElectrochemistryCatalysisElectron transferCombinatorial chemistrySurface modificationChemistryAnodeMoleculeLigand (biochemistry)NucleobasePhotochemistryNanotechnologyMaterials scienceOrganic chemistryElectrodePhysical chemistryExcited stateBiochemistryNuclear physicsDNAReceptorPhysicsFluorine in Organic ChemistryRadical Photochemical ReactionsCO2 Reduction Techniques and Catalysts