Reactivity of Nitroarenes toward Alkyl Radicals Enables Direct C–H Alkylation

Abstract. Friedel–Crafts alkylation is a cornerstone transformation for arene functionalization; however, strongly electron-deficient nitroarenes fail to u

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A generalized electrochemical dehydrogenation approach en route to α-phosphorylated amines

Given the widespread use of organophosphorus scaffolds in several disciplines, the formation of C(sp3)–P bonds is of fundamental importance. Direct access to α-phosphorylated amines still remains chal...

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Geminal Difunctionalization of Ketones via C─S Bond Insertion of Photogenerated Donor–Donor Diazo Compounds

Geminal difunctionalization of readily available building blocks provides rapid access to molecular complexity. This work introduces a strategy for installing two distinct functional groups on a carb...

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Photocatalytic Vanadium‐Mediated Amination of Benzene With Hydroxylamine

Photochemical activation of N-phenylphenothiazine (PPT) enables a selective direct benzene amination with hydroxylamine in the presence of various vanadium catalysts under mild reaction conditions. S...

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“On-water” photosensitization enables redox neutral acylation and alkylation of quinones - Nature Communications

Water-oil interfaces exhibit high cohesive energy density and form a supramolecular hydrogen-bonding network, which supports organic reactions in various ways. Here, the authors introduce the redox-ne...

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Divergent [3+2] Photocycloadditions of Nitrones to Isoxazolines and Oxa-Aza-Bicycloheptanes: Controlling Entry and Exit from Flatland | ChemRxiv

Three-dimensional, conformationally rigid molecular architectures are increasingly valued in chemical biology, and drug discovery, yet their syntheses often rely on step-intensive or metal-mediated methods. Herein, we report a metal-free, redox-neutral ...

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Predictive, Data‐Driven Design of Red‐Light Photoredox Catalysts for C─Heteroatom Bond Formation

From redox numbers to red light: Donor oxidation and core reduction potentials predict E0-0 in cyanoarene dyes, guiding selection of an efficient red-light catalyst, 4MeODPATPN (PC13). Under 620 nm l...

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Room-Temperature Copper Cross-Coupling Reactions of Anilines with Aryl Bromides

We present a novel copper-catalyzed method for aniline cross-couplings promoted by a 6-hydroxy picolinhydrazide ligand. The method achieves room-temperature reactivity with aryl bromides, enabled by a methanol/ethanol solvent mixture and a mild, functional group-compatible base, with catalyst loadings as low as 0.5 mol %. The use of industrially preferred solvents and base, as well as the high catalytic activity, offers a significant advancement in the practicality and scalability of industrial processes. Furthermore, the approach extends to the cross-coupling of aryl chlorides under elevated temperatures and demonstrates compatibility with additional nucleophile classes.

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Data Science-Assisted Workflow for Reaction Optimization in Process Chemistry

We present a newly developed, data-assisted workflow at Bayer that integrates Bayesian optimization (BO) with CIME4R, an open-source data visualization tool with explainable AI features, to facilitate...

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Flavin-Photocatalyzed Benzylic Functionalization, Spirocyclization, and Spiroepoxidation of Phenols

para-Quinone methides (p-QMs) are versatile, transient electrophilic dearomatized intermediates in organic synthesis, enabling a range of transformations, such as cycloadditions, nucleophilic addition...

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Photoexcited Manganese Complex of Abnormal N-Heterocyclic Carbene in Molecular Hydrogen Activation via Hydrogen Atom Transfer Pathway

In this work, we show that the innate reactivity of the photoexcited state of a Mn-hydride complex can be harnessed to design the activation of the H2 molecule for catalytic applications. Such activation of molecular hydrogen by a photoexcited heavier 5d metal (Ir) complex has recently been achieved; however, it has been realized with an earth-abundant and lighter 3d metal complex. Here, we demonstrate that an in situ-generated Mn–H complex of an abnormal N-heterocyclic carbene can activate molecular hydrogen upon photoexcitation. The key to this approach lies in the fact that ground-state manganese hydride absorbs light to undergo homolytic cleavage, generating a metalloradical (Mn·) and a hydrogen atom. This, in turn, enables the formation of an O–H bond upon reaction with an aldehyde. Simultaneously, the generated Mn· can activate the H2 molecule, reproducing the Mn–H species in its ground state along with a hydrogen atom. The trapping of important intermediates, such as Mn· species and associated radical intermediates, using spectroscopic techniques confirms the mechanistic proposal involving the excited state of the Mn complex.

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Harnessing Photochemistry in Natural Product Synthesis: From Strategy to Applications

Photochemistry and total synthesis are deeply rooted in the history of organic chemistry, each developing independently while also intersecting frequently. Indeed, mild reaction conditions, versatility of transformations, and complementary selectivities to thermal methods make photochemistry an especially powerful tool for the synthesis of complex target molecules. In this Review, we highlight recent examples of total syntheses (from 2020 to 2025) featuring photochemical reactions as pivotal steps. Although the application of photochemistry in total synthesis has been consistently reviewed throughout the past decades, we feel that the wider emergence of photocatalytic methods, together with the continued importance of certain direct irradiation approaches, warrants its own discussion. We hope that our analytical approach and strategic insights will help us to identify cases where photochemical reactions could prove useful, thereby further encouraging their use in total syntheses.

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Synthesis of α-Amino Acids by ConPET-Mediated CO2 Fixation into Amides

Herein, we report a photocatalytic method for the selective functionalization of α-C(sp3)-H bonds adjacent to the nitrogen atom in amides. By harnessing a synergistic combination of hydrogen atom transfer (HAT), consecutive photoinduced electron transfer (ConPET), and reductive radical-polar crossover, we efficiently incorporated high-value electrophiles, including CO2, 13CO2, and deuterium, at the α-N position. The transformation proceeds in moderate to high yields across a diverse range of amides, representing a significant advancement in both isotopically labeled α-amino acid synthesis and amide deuteration.

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Photoredox/Nickel Dual Catalytic C(sp2)S Cross‐coupling of Bromoanilines Enabled by Mineral Acids

Mineral acids promote nickel-catalyzed C(sp2)<span class='icomoon'></span>S cross-coupling of bromoanilines and related amine-containing electrophiles with thiols by protonating free amines, thereby facilitating oxidative addit...

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Fully Sensitized Upconversion Nanoparticles as Efficient Catalysts for NIR‐Driven UV Photochemistry

Engineered NaYbF4:Tm3+@NaYF4 nanoparticles, featuring a fully sensitized Yb3+ lattice and an optimized core–shell architecture, convert five 980 nm photons by sequential absorption into a single 345 ...

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Photoswitches beyond azobenzene: a beginner’s guide

Beilstein Journal of Organic Chemistry

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Generalizing Vinyl Halide Cross‐Coupling Reactions with Photoredox and Photoredox/Nickel Dual Catalysis

A general strategy has been developed for predictable and robust vinyl halide cross-coupling reactions. This approach demonstrates broad applicability across seven distinct bond-forming transformatio...

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Photo-Catalyzed Synthesis of Indanones from Aromatic Aldehydes and Terminal Alkynes

Indanones are key structural motifs in pharmaceuticals and bioactive natural products, making their efficient synthesis a subject of continued interest. Conventional methods typically rely on transiti...

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Expanding the Repertoire of Photoswitchable Unnatural Amino Acids for Enzyme Engineering

Enzyme engineering with photoswitchable unnatural amino acids (psUAAs) has a high potential for applications such as biocatalysis. Here, we extend the current repertoire of psUAAs to include more ver...

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Alternative Mechanism of Enzymatic Photocontrol by Azobenzene

Azobenzene is a widely recognized tool for achieving artificial spatiotemporal control of enzyme activity through the use of light. Photocontrol reversibility is typically based on photostationary sta...

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Magnetic Stirring May Cause Irreproducible Results in Chemical Reactions

Magnetic stirrers, the most widely used and ubiquitous devices for performing chemical reactions in laboratory settings, may cause reproducibility problems. Reproducibility in a range of chemical proc...

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Green‐light Cerium Photocatalysis enabled by Pyridine N‐oxide Ligands

Abstract: We report pyridine N-oxides as neutral ligands in cerium photocatalysis. By using those neutral ligands, photoactive Ce(IV)-species are generated, that show an extensive bathochromic shift ...

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Reactivity of Superbasic Carbanions Generated via Reductive Radical‐Polar Crossover in the Context of Photoredox Catalysis

Photocatalytic reactions with a reductive radical-polar crossover (RRPCO) involve intermediates with carbanionic reactivity. These are best described as free carbanions. Reactions with such carbanion...

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Anthraquinone Sulfonates as Water‐Soluble Photocatalysts: Synthetic Applications and Perspectives

The development of photochemistry in water is rapidly advancing, and the demand for water-soluble photocatalysts is increasing. Accordingly, anthraquinone sulfonates are interesting options for the a...

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