In recent years, the integration of photocatalytic hydrogen atom transfer (HAT) with transition metal catalysis has emerged as a formidable strategy for the construction of C(sp3)–carbon and C(sp3)-hetero bonds. The fusion of these two methodologies has been utilized widely in organic synthesis, leading to new transformations in chemical synthesis. In this review, we aim to summarize the recent advances made in sp3 C–H functionalizations through photocatalytic HAT followed by transition metal catalysis. Our focus will be on the diverse strategies and their synthetic applications, in addition to detailed mechanisms involved in these reactions. An in-depth understanding of these mechanisms is crucial for the rational design of new catalysts and reaction conditions to further enhance the efficiency of these transformations. We hope that this review will serve as a valuable resource for researchers in the area of metallaphotoredox catalysis, and will inspire the further development of this application in green chemistry, drug synthesis, material science, and other related fields.
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