Over the past decade, photocatalysis has emerged as one of the frontiers in organic chemistry, attracted tremendous interest from the synthetic community. Compared to traditional methods, photocatalytic reactions offer advantages such as mild conditions, high functional group tolerance and unique reactivity and selectivity. As an important area of photocatalysis, the transformation of imines is undergoing continuous advancements. Under photocatalytic conditions, the reactivity of imines is reshaped, allowing them to undergo single-electron reduction to form α-aminoalkyl radicals—a process that can even reverse their polarity, enabling them to act as carbon nucleophiles. N-heterocycles and amines are among the most prevalent and important organic compounds, which are found in numerous alkaloids and pharmaceutical molecules. Therefore, the conversion of imine compounds to amines under photocatalytic conditions have introduced new methodologies to solve important problems in the synthesis of drugs and beyond, which were hardly achieved by traditional synthetic strategies. This review summarized the research progress on the photocatalytic synthesis of amines from imines via α-aminoalkyl radicals, with a focus on selectivity and functional group tolerance.

Key words: photocatalysis, imine, amine, radical