To support the presence of radical intermediates, the reaction was conducted in the presence of radical scavengers such as TEMPO or BHT, leading to no product formation in both cases (Scheme S8, Experiment-1 to 3). In presence of BHT, the coupling product between the α-amino radical (III) and BHT was detected to a small extent by HRMS (Fig. , Experiment-I), further confirming its formation. Moreover, the α-amino radical could be efficiently trapped with Michael acceptors such as acrylonitrile (Scheme-S8, Experiment-4 to 5). In presence of D2O, deuterium was, as expected, incorporated in α-position to the nitrile, supported by HRMS and NMR (Fig. and Fig. , Experiment-II).