Tao Shen1, Tristan H Lambert2. 1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA. 2. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14850, USA. tristan.lambert@cornell.edu.
Abstract
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.
The conversion of unactivated n class="Chemical">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 arenescan 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.
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