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Electrophotocatalysis (EPC) has evolved as a new scientific discipline around the boundary of highly active fields: electrochemistry and photocatalysis. EPC allows us to combine the energy of light and electric potential to activate previously inaccessible compounds via single-electron transfer (SET). Herein, we review the most essential applications of EPC to the C-H functionalization of molecules. This work discusses mechanisms that can be encountered when designing such processes and analyzes technical aspects of performing EPC reactions in the laboratory.

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We report a practical and sustainable electrophotochemical metal-catalyzed protocol for decarboxylative cyanation of simple aliphatic carboxylic acids. This environmentally friendly method features easy availability of substrates, broad functional group compatibility, and directly converts a diverse range of aliphatic carboxylic acids including primary and tertiary alkyl acids into synthetically versatile alkylnitriles without using chemical oxidants or costly cyanating reagents under mild reaction conditions.

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The ion extraction and electro/photo catalysis are promising methods to address environmental and energy issues. Covalent organic frameworks (COFs) are a class of promising template to construct absorbents and catalysts because of their stable frameworks, high surface areas, controllable pore environments, and well-defined catalytic sites. Among them, ionic COFs as unique class of crystalline porous materials, with charges in the frameworks or along the pore walls, have shown different properties and resulting performance in these applications with those from charge-neutral COFs. In this review, current research progress based on the ionic COFs for ion extraction and energy conversion, including cationic/anionic materials and electro/photo catalysis is reviewed in terms of the synthesis strategy, modification methods, mechanisms of adsorption and catalysis, as well as applications. Finally, we demonstrated the current challenges and future development of ionic COFs in design strategies and applications.

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The merging of transition metal catalysis with electrochemistry has become a powerful tool for organic synthesis because catalysts can govern the reactivity and selectivity. However, coupling catalysts with alkyl radical species generated by anodic oxidation remains challenging because of electrode passivation, dimerization, and overoxidation. In this study, we developed convergent paired electrolysis for the coupling of nickel catalysts with alkyl radicals derived from photoinduced ligand-to-metal charge-transfer of cyclic alcohols and iron catalysts, providing a practical method for site-specific and remote arylation of ketones. The synergistic use of photocatalysis with convergent paired electrolysis can provide alternative avenues for metal-catalyzed radical coupling reactions.

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Electrophotocatalytic transformations are garnering attention in organic synthesis, particularly for accessing reactive intermediates under mild conditions. Moving these methodologies to continuous-flow systems, or flow ElectroPhotoCatalysis (f-EPC), showcases potential for scalable processes due to enhanced irradiation, increased electrode surface, and improved mixing of the reaction mixture. Traditional methods sequentially link photochemical and electrochemical reactions, using flow reactors connected in series, yet struggle to accommodate reactive transient species. In this study, we introduce a new flow reactor concept for electrophotocatalysis (EPC) that simultaneously utilizes photons and electrons. The reactor is designed with a transparent electrode and employs cost-effective materials. We used this technology to develop an efficient process for electrophotocatalytic heteroarylation of C(sp3 )-H bonds. Importantly, the same setup can also facilitate purely electrochemical and photochemical transformations. This reactor represents a significant advancement in electrophotocatalysis, providing a framework for its application in flow for complex synthetic transformations.

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In contrast to the rapid growth of electrophotocatalysis in recent years, enantioselective catalytic reactions powered by this unique methodology remain rare. In this work, we report an electrophotochemical metal-catalyzed protocol for direct asymmetric decarboxylative cyanation of aliphatic carboxylic acids. The synergistic merging of electrophotochemical cerium catalysis and asymmetric electrochemical copper catalysis permits mild reaction conditions for the formation and utilization of the key carbon centered radicals by combining the power of light and electrical energy. Electrophotochemical cerium catalysis enables radical decarboxylation to produce alkyl radicals, which could be effectively intercepted by asymmetric electrochemical copper catalysis for the construction of C-CN bonds in a highly stereoselective fashion. This environmentally benign method smoothly converts a diverse array of arylacetic acids into the corresponding alkyl nitriles in good yields and enantioselectivities without using chemical oxidants or pre-functionalization of the acid substrates and can be readily scaled up.

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An electrophotochemical dual metal-catalyzed protocol for decarboxylative arylation of simple aliphatic carboxylic acids with aryl halides is reported. The relative stabilities of catalytically active metal complexes simultaneously generated at anode and cathode are the key design elements for the success of this convergent paired electrolysis. This new electrophotocatalytic method is mild, robust, and most importantly, capable of accommodating simple primary aliphatic acids including acetic acid - ubiquitous and variegated structural motifs yet remain oddly challenging substrates - directly as native functional groups for decarboxylative C(sp2 )-C(sp3 ) bond formation.

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Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single-electron transfer (SET) reactions in a much greener way and broadens the redox window of possible transformations. Herein, the most recent contributions are reviewed, demonstrating exciting new opportunities, namely, the combination of PEC with other reactivity paradigms (hydrogen-atom transfer, radical polar crossover, energy transfer sensitization), scalability up to multigram scale, novel selectivities in SET super-oxidations/reductions and the importance of precomplexation to temporally enable excited radical ion catalysis.

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The Minisci alkylation of N-heteroarenes with unactivated alkanes under external oxidant-free conditions provides an economically attractive route to access alkylated N-heteroarenes but remains underdeveloped. Herein, a new electrophotocatalytic strategy to access alkyl radicals from strong C(sp3 )-H bonds was reported for the following Minisci alkylation reactions in the absence of chemical oxidants. This strategy realized the first example of cerium-catalyzed Minisci alkylation reaction directly from abundant unactivated alkanes with excellent atom economy. It is anticipated that the general design principle would enrich catalytic strategies to explore the functionalizations of strong C(sp3 )-H bonds under external oxidant-free conditions with H2 evolution.

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Herein, we disclose that electrochemical stimulation induces new photocatalytic activity from a range of structurally diverse conventional photocatalysts. These studies uncover a new electron-primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2 )-N and C(sp2 )-O bonds. We illustrate several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employ electrochemical current measurements to perform a reaction progress kinetic analysis. This technique reveals that the improved activity of this new system is a consequence of an enhanced catalyst stability profile.

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The electrophotocatalytic heterofunctionalization of arenes is described. Using 2,3-dichloro-5,6-dicyanoquinone (DDQ) under a mild electrochemical potential with visible-light irradiation, arenes undergo oxidant-free hydroxylation, alkoxylation, and amination with high chemoselectivity. In addition to batch reactions, an electrophotocatalytic recirculating flow process is demonstrated, enabling the conversion of benzene to phenol on a gram scale.

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Organic radicals are versatile synthetic intermediates that provide reactivities and selectivities complementary to ionic species. Despite its long history, electrochemically driven radical reactions remain limited in scope. In the past few years, there have been dramatic increase in research activity in organic electrochemistry. We have been developing electrochemical and electrophotocatalytic methods for the generation and synthetic utilization of organic radicals. In our studies, various radical species such as alkene and arene radical cations and carbon- and heteroatom-centered radicals are generated from readily available precursors through direct electrolysis, molecular electrocatalysis or molecular electrophotocatalysis. These radical species undergo various inter- and intramolecular oxidative transformations to rapidly increase molecular complexity. The simultaneous occurrence of anodic oxidation and cathodic proton reduction allows the oxidative reactions to proceed through H2 evolution without external chemical oxidants.

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The electrophotocatalytic SN Ar reaction of unactivated aryl fluorides at ambient temperature without strong base is demonstrated.

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Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions. Here, these two modalities are combined in an electrophotocatalytic oxidation platform. This chemistry employs a trisaminocyclopropenium (TAC) ion catalyst, which is electrochemically oxidized to form a cyclopropenium radical dication intermediate. The radical dication undergoes photoexcitation with visible light to produce an excited-state species with oxidizing power (3.33 V vs. SCE) sufficient to oxidize benzene and halogenated benzenes via single-electron transfer (SET), resulting in C-H/N-H coupling with azoles. A rationale for the strongly oxidizing behavior of the photoexcited species is provided, while the stability of the catalyst is rationalized by a particular conformation of the cis-2,6-dimethylpiperidine moieties.

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