Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration of aliphatic C-H bonds. In this manifold, a photocatalyst (PC_HAT) exploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds. Selective C-H bond elaboration may be achieved by a judicious choice of the hydrogen abstractor (key parameters are the electronic character and the molecular structure), as well as reaction additives. Different are the classes of PCs_HAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, a metal-oxo porphyrin and a tris(amino)cyclopropenium radical dication. The processes (mainly C-C bond formation) are in most cases carried out under mild conditions with the help of visible light. The aim of this review is to offer a comprehensive survey of the synthetic applications of photocatalyzed d-HAT.

Photocatalysis (by semiconductors, molecules and ions) is used in such diverse applications as water hydrolysis for producing hydrogen as fuel, organic synthesis and the recovery of polluted effluents. This tutorial review discusses the common principles of such applications and their role in green chemistry.

In the reactions reviewed, an organic molecule under irradiation catalyzes a chemical reaction. The activation is based either on hydrogen or on electron transfer. Commonly used photoorganocatalysts are aromatic ketones, quinones, heterocycles, dyes; intermediates formed are radicals, radical ions and ions from precursors such as alkanes, alkenes, amines, ethers etc. Oxidation (mainly oxygenation) and reduction processes are obtained along with the α-functionalization of amines and ketones, conjugate additions, cycloadditions etc. The key characteristic of the method is the smooth generation of highly reactive intermediates under mild conditions.

The adoption of hydrogen atom transfer (HAT) in a photocatalytic approach, in which an excited catalyst is responsible for substrate activation, offers unique opportunities in organic synthesis, enabling the straightforward activation of R–H (R = C, Si, S) bonds in desired reagents. Either a direct strategy, based on the intrinsic reactivity of a limited number of photocatalysts in the excited state, or an indirect one, in which a photocatalytic cycle is used for the generation of a thermal hydrogen abstractor, can be exploited. This microreview summarizes the most recent advances (mainly from the last two years) in this rapidly developing area of research, collecting the selected examples according to the nature of the species promoting the HAT process. From the synthetic point of view, this area has led to the development of a plethora of strategies for C–C, C–Si, C–N, C–S, and C–halogen (particularly, fluorine) bond formation, as well as for oxidation reactions.