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Ligand-Directed Selective Protein Modification Based on Local Single-Electron-Transfer Catalysis


  • This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Chemical Biology of Natural Products” from The Ministry of Education, Culture, Sports, Science and Technology (Japan).


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A photocatalyst ([Ru(bpy)3]2+) bound to a protein ligand was essential for the title method. Local single-electron transfer from the catalyst resulted in the formation of tyrosyl radicals. N′-Acetyl-N,N-dimethyl-1,4-phenylenediamine was used as the tyrosyl radical trapping agent and used in a radical addition to afford selective modification of the target protein.