Electrophotocatalytic diamination of vicinal C-H bonds.

The conversion of unactivated carbon-hydrogen (C-H) bonds to carbon-nitrogen (C-N) bonds is a highly valued transformation. Existing strategies typically accomplish such reactions at only a single C-H site because the first derivatization diminishes the reactivity of surrounding C-H bonds. Here, we show that alkylated arenes can undergo vicinal C-H diamination reactions to form 1,2-diamine derivatives through an electrophotocatalytic strategy, using acetonitrile as both solvent and nitrogen source. The reaction is catalyzed by a trisaminocyclopropenium (TAC) ion, which undergoes anodic oxidation to furnish a stable radical dication while the cathodic reaction reduces protons to molecular hydrogen. Irradiation of the TAC radical dication (wavelength of maximum absorption of 450 to 550 nanometers) with a white-light compact fluorescent light generates a strongly oxidizing photoexcited intermediate. Depending on the electrolyte used, either 3,4-dihydroimidazole or aziridine products are obtained. Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Citation

Tao Shen, Tristan H Lambert. Electrophotocatalytic diamination of vicinal C-H bonds. Science (New York, N.Y.). 2021 Feb 05;371(6529):620-626

PMID: 33542135

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