Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as the sole energy input. Following this dual-functional photocatalytic strategy, a dreamlike reaction pathway for constructing C-C/C-X (X = C, N, O, S) bonds from abundant and readily available X-H bond-containing compounds with concomitant release of H2 can be readily fulfilled without the need of external chemical reagents, thus offering a green and fascinating organic synthetic strategy. In this review, we begin by presenting a concise overview on the general background of traditional photocatalytic H2 production and then focus on the fundamental principles of cooperative photoredox coupling of selective organic synthesis and H2 production by simultaneous utilization of photoexcited electrons and holes over semiconductor-based catalysts to meet the economic and sustainability goal. Thereafter, we put dedicated emphasis on recent key progress of cooperative photoredox coupling of H2 production and various selective organic transformations, including selective alcohol oxidation, selective methane conversion, amines oxidative coupling, oxidative cross-coupling, cyclic alkanes dehydrogenation, reforming of lignocellulosic biomass, and so on. Finally, the remaining challenges and future perspectives in this flourishing area have been critically discussed. It is anticipated that this review will provide enlightening guidance on the rational design of such dual-functional photoredox reaction system, thereby stimulating the development of economical and environmentally benign solar fuel generation and organic synthesis of value-added fine chemicals.

Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts.

The fields of C-H functionalization and photoredox catalysis have garnered enormous interest and utility in the past several decades. Many different scientific disciplines have relied on C-H functionalization and photoredox strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, and fine chemical synthesis. In this Review, we highlight the use of photoredox catalysis in C-H functionalization reactions. We separate the review into inorganic/organometallic photoredox catalysts and organic-based photoredox catalytic systems. Further subdivision by reaction class-either sp2 or sp3 C-H functionalization-lends perspective and tactical strategies for use of these methods in synthetic applications.

Photoredox-Catalyzed C-H Functionalization Reactions.

Photocatalytic production of solar fuels from CO2 is a promising strategy for addressing global environmental problems and securing future energy supplies. Although extensive research has been conducted to date, numerous impediments to realizing efficient, selective, and stable CO2 reduction have yet to be overcome. This comprehensive review highlights the recent advances in CO2 photoreduction, including critical challenges such as light-harvesting, charge separation, and the activation of CO2 molecules. We present promising strategies for enhancing the photocatalytic activities and discuss theoretical insights and equations for quantifying photocatalytic performance, which are expected to afford a fundamental understanding of CO2 photoreduction. We then provide a thorough overview of both traditional photocatalysts such as metal oxides and state-of-the-art catalysts such as metal–organic frameworks and 2D materials, followed by a discussion of the origin of carbon in CO2 photoreduction as a means to further understand the reaction mechanism. Finally, we discuss the economic viability of photocatalytic CO2 reduction before concluding the review with proposed future research directions.

Solar fuels: research and development strategies to accelerate photocatalytic CO2 conversion into hydrocarbon fuels

Photocatalytic CO 2 conversion is vital technology to realize global carbon neutrality and generate future energy supplies. This review proposes fundamentals, challenges, strategies, and prospects for photocatalytic CO 2 conversion research. 

Solar fuels: research and development strategies to accelerate photocatalytic CO<sub>2</sub> conversion into hydrocarbon fuels

Heteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative cross-coupling of heteroarenes with aliphatic C-H bonds provides straightforward access to functionalized heteroarenes from readily available materials. Established methods employ stoichiometric chemical oxidants under conditions of heating or light irradiation. By merging electrochemistry and photochemistry, we have achieved efficient photoelectrochemical dehydrogenative cross-coupling of heteroarenes and C(sp3 )-H donors through H2 evolution, without the addition of metal catalysts or chemical oxidants. Mechanistically, the C(sp3 )-H donor is converted to a nucleophilic carbon radical through H-atom transfer with chlorine atom, which is produced by light irradiation of anodically generated Cl2 from Cl- . The carbon radical then undergoes radical substitution to the heteroarene to afford alkylated heteroarene products.

Scalable Photoelectrochemical Dehydrogenative Cross‐Coupling of Heteroarenes with Aliphatic C−H Bonds

Quantum dots enable direct alkylation and arylation of allylic C(sp3)–H bonds with hydrogen evolution by solar energy

Direct allylic C-H thiolation is straightforward for allylic C(sp3 )-S bond formation. However, strong interactions between thiol and transition metal catalysts lead to deactivation of the catalytic cycle or oxidation of sulfur atom under oxidative condition. Thus, direct allylic C(sp3 )-H thiolation has proved difficult. Represented herein is an exceptional for direct, efficient, atom- and step-economic thiolation of allylic C(sp3 )-H and thiol S-H under visible light irradiation. Radical trapping experiments and electron paramagnetic resonance (EPR) spectroscopy identified the allylic radical and thiyl radical generated on the surface of photocatalyst quantum dots (QDs). The C-S bond formation does not require external oxidants and radical initiators, and hydrogen (H2 ) is produced as byproduct. When vinylic C(sp2 )-H was used instead of allylic C(sp3 )-H bond, the radical-radical cross-coupling of C(sp2 )-H and S-H was achieved with liberation of H2 . Such a unique transformation opens up a door toward direct C-H and S-H coupling for valuable organosulfur chemistry.

Direct Allylic C(sp3)−H and Vinylic C(sp2)−H Thiolation with Hydrogen Evolution by Quantum Dots and Visible Light

As one of the most ubiquitous bulk reagents available, the intrinsic chemical inertness of tetrahydrofuran (THF) makes direct and site-selective C(sp 3 )-H bond activation difficult, especially under redox neutral condition. Here, we demonstrate that semiconductor quantum dots (QDs) can activate α-C-H bond of THF via forming QDs/THF conjugates. Under visible light irradiation, the resultant alkoxyalkyl radical directly engages in radical cross-coupling with α-amino radical from amino C-H bonds or radical addition with alkene or phenylacetylene, respectively. In contrast to stoichiometric oxidant or hydrogen atom transfer reagents required in previous studies, the scalable benchtop approach can execute α-C-H bond functionalization of THF only by a QD photocatalyst under redox-neutral condition, thus providing a broad of value added chemicals starting from bulk THFs reagent. The high step- and atom-economy, high efficiency and broad substrate scope make the photocatalysis with QDs and visible light promising in both academic and industrial setting.

Direct, Site-Selective and Redox-Neutral α-C−H Bond Functionalization of Tetrahydrofurans via Quantum Dots Photocatalysis

The functionalization of aliphatic C-H bonds is both a major challenge and a desirable goal in organic synthesis. Here, we describe the successful arylation of unactivated alkanes with heteroarenes by using iridium polypyridyl complexes as the photocatalyst and persulfate as the HAT catalyst precursor under visible-light irradiation. This reaction features good functional group tolerance and broad scope with regard to both alkane and heteroarene substrates (37 examples), which allows direct access to alkyl-substituted N-heteroarenes, a key structural motif in natural products and bioactive molecules.

Direct Arylation of Unactivated Alkanes with Heteroarenes by Visible-Light Catalysis

Represented herein is the first example of N-radicals generation direct from N-H bonds activation under mild and redox-neutral conditions. The in-situ generated N-radical intercepts a reduced heteroarylnitrile/aryl halide for C-N bond formation under visible light irradiation of quantum dots (QDs). A series of aryl and alkylamines with heteroarylnitriles/aryl halides exhibit high efficiency, site-selectivity and good functional-group tolerance. Moreover, consecutive C-C and C-N bond formation using benzylamines as substrates is also achieved, producing N-aryl-1,2-diamines with H2 evolution. The redox-neutral conditions, broad substrate scope, and efficiency of N-radical formation are advantageous for organic synthesis.

Jia Qiao

Papers

Quantum dots enable direct alkylation and arylation of allylic C(sp3)–H bonds with hydrogen evolution by solar energy

Direct Allylic C(sp3)−H and Vinylic C(sp2)−H Thiolation with Hydrogen Evolution by Quantum Dots and Visible Light

Direct, Site-Selective and Redox-Neutral α-C−H Bond Functionalization of Tetrahydrofurans via Quantum Dots Photocatalysis

Direct Arylation of Unactivated Alkanes with Heteroarenes by Visible-Light Catalysis

Direct N-H Activation to Generate Nitrogen Radical for Arylamine Synthesis via Quantum Dots Photocatalysis.