Mangana(iii/iv)electro-catalyzed C(sp3)–H azidation |
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Authors: | Tjark H Meyer Ramesh C Samanta Antonio Del Vecchio Lutz Ackermann |
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Institution: | Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen Germany ; Woehler Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen Germany |
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Abstract: | Manganaelectro-catalyzed azidation of otherwise inert C(sp3)–H bonds was accomplished using most user-friendly sodium azide as the nitrogen-source. The operationally simple, resource-economic C–H azidation strategy was characterized by mild reaction conditions, no directing group, traceless electrons as the sole redox-reagent, Earth-abundant manganese as the catalyst, high functional-group compatibility and high chemoselectivity, setting the stage for late-stage azidation of bioactive compounds. Detailed mechanistic studies by experiment, spectrophotometry and cyclic voltammetry provided strong support for metal-catalyzed aliphatic radical formation, along with subsequent azidyl radical transfer within a manganese(iii/iv) manifold.The merger of manganese-catalyzed C–H functionalization with electrosynthesis enabled C(sp3)–H azidation devoid of chemical oxidants or photochemical irradiation. Detailed mechanistic studies are supportive of a manganese(iii/iv) electrocatalysis. |
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