Selective Functionalization of Hydrocarbons Using a ppm Bioinspired Molecular Tweezer via Proton-Coupled Electron Transfer
Hongyu Chen, Lingling Wang, Sheng Xu, Xiaohui Liu, Qian He, Lijuan Song, Hongbing Ji
Abstract
An expanded porphyrin-biscopper hexaphyrin was introduced as a bioinspired molecular tweezer to co-catalyze functionalization of C(sp3)–H bonds. Theoretical and experimental investigations suggested that the biscopper hexaphyrin served as a molecular tweezer to mimic the enzymatic orientation/proximity effect, efficiently activating the N-hydroxyphthalimide (NHPI) via light-free proton-coupled electron transfer (PCET), at an exceptionally low catalyst loading of 10 mol ppm. The resulting N-oxyl radical (PINO) was versatile for chemoselective C–H oxidation and amination of hydrocarbons.
Topics & Concepts
Surface modificationAminationChemistryPorphyrinProton-coupled electron transferCatalysisElectron transferPhotochemistryProtonCombinatorial chemistryOrganic chemistryPhysical chemistryPhysicsQuantum mechanicsPorphyrin and Phthalocyanine ChemistryMetal-Catalyzed Oxygenation MechanismsOxidative Organic Chemistry Reactions