Self-detachable protecting group function of CO2 in the electrochemical reduction of aryl azides

A unique self-detachable protecting group function of CO2 in the selective electrochemical reduction of azides is discovered. By utilizing CO2 as the self-detachable protecting group, the selective reduction of azides to primary amines is successfully achieved. In contrast, in the absence of CO2, azides undergo a preferential transformation into formamide derivatives. Due to its stronger electrophilicity than DMF, CO2 preferentially accepts the nucleophilic attack of N˙ˉ generated in situ under electrochemical reduction conditions, thus passivating the nucleophilic ability of the N-site and preventing the formylation process. The function of self-detachable protecting group is achieved as CO2 is ultimately released through the spontaneous decarboxylation process, and this process does not need to add deprotection agent. This study also proposes the generation of N˙ˉ through electrochemical reduction of azide. The current findings demonstrate an unconventional application of CO2, which will stimulate the exploration of novel roles for CO2 as a non-C1 synth in electrosynthesis.

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