Metallaphotoredox catalysis merging photocatalysis and transition metal catalysis is now the most efficient platform for sp³ C–H functionalizations due to its very efficient activation and transformation capability. In such a process, photocatalysis is usually in charge of C–H bond activation to generate an sp³-hybridized carbon-centred radical, whereas transition metal catalysis is in charge of the subsequent transformation of this radical. Here we review advances in sp³ C–H functionalizations under matallaphotoredox catalysis via photocatalytic single-electron transfer mechanisms as opposed to hydrogen atom transfer processes. The delineation of these advancements is initially organized according to distinct sp³ C–H bonds and subsequently categorized by various transition metal catalytic systems. We encompass a thorough exploration of diverse metallaphotoredox catalysis strategies, along with their synthetic applications and mechanisms. Similarities and differences between these strategies are described to inspire new reaction designs, thus promoting further development of this field.

金属光氧化还原催化结合了光催化和过渡金属催化，由于其非常有效的活化和转化能力，现在是sp ³ C–H 官能化最有效的平台。在这样的过程中，光催化通常负责C-H键活化以产生sp ³杂化的碳中心自由基，而过渡金属催化负责该自由基的后续转化。在这里，我们回顾了在 matallaphotoredox 催化下通过光催化单电子转移机制（而不是氢原子转移过程）进行sp ³ C-H 官能化的进展。这些进展的描述最初是根据不同的sp ³ C-H 键组织的，随后根据各种过渡金属催化系统进行分类。我们对各种金属光氧化还原催化策略及其合成应用和机制进行了彻底的探索。这些策略之间的异同被描述以激发新的反应设计，从而促进该领域的进一步发展。