The photoredox reactions involving electron donor-acceptor (EDA) complexes have attracted significant attentions in the last decade. Very recently, the sodium iodide-triphenylphosphine-N-acyloxyphthalimide EDA complex has been discovered and employed in developing several net redox-neutral photoreactions. Herein, the EDA complex has been applied in a net reductive setup for the first time to establish a photoredox alkylation of aldimines without photosensitizer. The reaction affords not only high yields for secondary, tertiary andα-heterosubstituted alkyl radicals, but also high yields for primary alkyl radicals, and moderate to high yields for electron-rich or secondary benzylic radicals, two difficult groups of radicals in previous studies. This work provides an efficient and reliable approach for the synthesis of unnatural amino acids and amines.

Key words: photoredox, aldimine, electron donor-acceptor complex