Visible-light photocatalysis has evolved over the last decade into a widely used method in organic synthesis. Photocatalytic variants have been reported for many important transformations, such as cross-coupling reactions, α-amino functionalizations, cycloadditions, ATRA reactions, or fluorinations. To help chemists select photocatalytic methods for their synthesis, we compare in this Review classical and photocatalytic procedures for selected classes of reactions and highlight their advantages and limitations. In many cases, the photocatalytic reactions proceed under milder reaction conditions, typically at room temperature, and stoichiometric reagents are replaced by simple oxidants or reductants, such as air, oxygen, or amines. Does visible-light photocatalysis make a difference in organic synthesis? The prospect of shuttling electrons back and forth to substrates and intermediates or to selectively transfer energy through a visible-light-absorbing photocatalyst holds the promise to improve current procedures in radical chemistry and to open up new avenues by accessing reactive species hitherto unknown, especially by merging photocatalysis with organo- or metal catalysis.

The synthesis of β-hydroxysulfones from sulfonyl chlorides and styrenes in the presence of water by a visible light mediated atom transfer radical addition (ATRA)-like process utilizing fac[Ir(ppy)3] as photoredox catalyst was developed in high yields. This process could be combined with the visible light mediated synthesis of trifluoromethylated sulfonyl chlorides via an ATRA reaction between alkenes and CF3SO2Cl utilizing [Cu(dap)2Cl] as photoredox catalyst, demonstrating the possibility of sequential photoredox processes.

An efficient method for the synthesis of substituted cyclobutanes from cinnamates, chalcones, and styrenes has been developed utilizing a visible-light triplet sensitisation mode. This reaction provides a diverse range of substituted cyclobutanes in high yields under mild conditions without the need of external additives. Good regioselectivity is obtained due to strong π-π-stacking of arene moieties, whereas diastereoselectivity relies on the electronic effects or ortho-substitution of the arene substrate. The utility of this transformation is demonstrated by the formal synthesis of the lignane natural product (±)-Tanegool.

A visible-light-induced photocatalytic method for the arylsulfonylation of heterocycles has been developed. The synthetic utility of this reaction is reflected by the direct use of commercially available sulfonyl chlorides and heterocycles under room temperature conditions. Complementarily, the photocatalytic arylation of heterocycles by sulfonyl chlorides via extrusion of SO is feasible at elevated temperature conditions, allowing switching between arylation or arylsulfonylation with excellent chemoselectivity.

Conspectus Over the past decade, photoredox catalysis has blossomed as a powerful methodology because of its wide applicability in sustainable free-radical-mediated processes, in which light is used as a cleaner energy source to alter the redox properties of organic molecules and to drive unique chemical transformations. Numerous examples of highly selective C–C and C–heteroatom bond formation processes have been achieved this way in an efficient and waste-reducing way. Therein, the activation of widely available organic halides via single-electron reduction has been broadly applied for organic synthesis. However, in comparison with alkyl and aryl halides, the analogous utilization of vinyl halides is less developed, most likely as a consequence of the highly unstable vinyl radicals generated as intermediates along with their strong tendency to abstract hydrogen atoms from a suitable source (e.g., the solvent), resulting in a synthetically less useful reduction. Nevertheless, during the last years, a number of photocatalytic processes involving vinyl halides have been developed, featuring the generation of vinyl radicals, diradicals, or radical cations as the key transient species. Moreover, photoredox processes in which a radical reacts with a vinyl halide or with an in situ-generated vinylmetal halide have been developed. Thus, identifying suitable conditions to generate and manipulate these reactive species has resulted in novel synthetic processes in a controllable manner. Moreover, in view of the great versatility of vinyl halides in palladium-catalyzed cross-coupling reactions, their activation by visible light might provide an attractive alternative to such processes, especially when non-noble metals could be used as photoinitiators in the future. In this Account, we discuss the various strategies of photoredox processes involving vinyl halides, classifying the material into four categories: (a) formation of a vinyl radical upon receipt of an electron from the photocatalyst, (b) formation of a radical cation after donation of an electron to the photocatalyst, (c) energy transfer corresponding to diradical formation upon triplet–triplet sensitization, and (d) dual transition metal and photocatalysis employing vinyl halides as precursors. While in the first three approaches the activation of vinyl halides is part of the photochemical step, the fourth one involves the interaction of a photochemically generated radical with a vinylnickel­(II) halide obtained in turn by the oxidative addition of nickel(0) to the vinyl halide. Therefore, we highlight these important developments for conceptual comparison to the direct activation of vinyl halides by light, but they are not covered in depth in this Account.