N-Heterocyclic carbenes (NHCs) are unique Lewis basic catalysts that mediate various organic transformations by means of polarity reversal. Although the scope of research on two-electron reactions mediated by NHC catalysts has been expanding, the types of these reactions are limited by the inability of NHCs to engage sp3-electrophiles. However, the revival of photocatalysis has accelerated the development of free-radical chemistry, and combining photoredox catalysis and NHC catalysis to achieve NHC-mediated radical reactions under mild conditions could overcome the above-mentioned limitation. This review summarizes recent advances in combining photoredox and NHC catalysis, focusing on elucidation and exploration of mechanisms, with the aim of identifying challenges and opportunities to develop more types of catalytic models.
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