Development of strategies for the direct C—H functionalization of nitrogen-containing compounds are in high demand for a variety of applications. This work displays a novel method for the C—H functionalization of carbamate-protected secondary amines invoking photoredox-generated α-carbamyl radicals as the key reactive intermediate. The use of the highly oxidizing, organic-based acridinium photoredox allows for direct oxidation of the normally difficult to access carbamate protected amines to give the corresponding carbamyl radical cation (see figure). These open-shell species, after deprotonation can be captured using a variety of Michael acceptors to give elaborate α-functionalized secondary amines (see figure). The reaction proceeds under mild conditions without the requirment of exogenous redox mediators or substrate prefunctionalization.

Generation and capture of α–carbamyl radicals using organic photoredox catalysis

256th National Meeting (2018)

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