Cobalt in the Spotlight: Advances in Photocatalytic Cross‐Coupling Reactions

Cobalt-mediated photocatalytic cross-coupling has emerged as a powerful strategy for sustainable bond construction. This review highlights recent advances in visible-light-driven cobalt–photoredox du...

chemistry-europe.onlinelibrary.wiley.com

Riboflavin Photocatalyzed Synthesis of 1,2‐diarylbenzimidazoles From <i>N</i>,<i>N</i>’‐diarylbenzimidamides

A metal-free visible-light strategy enables the synthesis of 1,2-diarylbenzimidazoles via riboflavin-based photocatalysis under mild conditions. Mechanistic and computational studies reveal a PCET-dr...

chemistry-europe.onlinelibrary.wiley.com

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Counterion Effects on the Properties and Reactivity of Charged Photoredox Catalysts

The choice of a counterion for a charged photocatalyst has long been overlooked. In this review, we summarize recent reports on counterion effects in photocatalysis, providing readers with a comprehe...

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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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Anomeric Amide Enabled Divergent Synthesis of Unsymmetrical Ureas, Carbamates, Thioesters, and Amides From Aldehydes

An anomeric amide-enabled divergent aldehyde functionalization sequence provides one-pot access to unsymmetrical ureas, carbamates, thiocarbamates, thioesters, and amides. Key to this transformation ...

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Triple energy transfer-enabled dearomative cycloaddition/rearrangement cascade of bicyclic azaarenes to structurally complex products - Nature Catalysis

Energy transfer (EnT) catalysed dearomative cycloadditions of bicyclic azaarenes are largely limited to [4+2] pathways, with higher-order cycloadditions being difficult to achieve. Now, the authors ci...

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Accessing Medium-Sized Bridged Heterocycles via EnT-Catalyzed Intermolecular Dearomative (5 + 4) Cycloaddition of Furans and Oxazoles

Medium-sized bridged heterocycles are highly attractive structural motifs in bioactive natural products and medicinal chemistry. However, their broader exploration remains limited due to the lack of concise and modular synthetic strategies, as their synthesis is challenged by unfavorable enthalpic and entropic constraints. Herein, we report an energy transfer (EnT)-catalyzed intermolecular (5 + 4) dearomative cycloaddition of furans with vinyl cyclopropanes, providing direct access to (Z)-10-oxabicyclo[5.2.1]deca-3,8-diene scaffolds in a single step. Visible light triplet sensitization unlocks a distinct diene-type 1,4-biradical activation mode in furans. This triplet-state reactivity enables intermolecular higher-order (5 + 4) cycloadditions that remain inaccessible under conventional thermal activation. Mechanistic investigations support an energy transfer pathway and provide insights into the origin of the observed regioselectivity. The resulting partially unsaturated cycloadducts offer multiple synthetic handles for downstream functionalization, enabling rapid and modular incorporation of heterobicyclo[5.2.1]alkane motifs and highlighting their potential as versatile building blocks in synthetic chemistry.

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Phosphoryl Radicals from Trivalent Iminyl Phosphines: A Photocatalytic Approach to N‐Phosphoryl Azetidines

Photochemically generated phosphoryl radicals from iminyl phosphines enable strain-release addition to azabicyclobutanes, providing access to elusive N-phosphoryl azetidines. Combined experimental, c....

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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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In Situ Construction of Imidazopyridinium Fluorescent Labels for Bioconjugation

Chromophore engineering of isoquinoline aldehydes generates TICT-based fluorogenic dyes for in situ labeling of diverse (bio)molecules with large Stokes shifts compatible with cell imaging.

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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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Diastereoselective Synthesis of Housanes via the Carbocupration of Cyclopropenes

Strained bicyclic frameworks have emerged as valuable isosteric replacements and synthetic platforms based on strain-driven reactivity. The bicyclo[2.1.0]pentane, “housane”, a highly strained, nonsymm...

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Accessing CF3-Cyclopropenes ─ A Platform for the Synthesis of Trifluoromethylated Building Blocks

Cyclopropenes are the smallest unsaturated carbocycles. They possess exceptionally high ring strain, resulting in unique reactivity, enabling C═C bond functionalization and ring-opening transformation...

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Synthesis of Cobalt-Centered Inorganic Sandwich Complexes

Complete inorganic sandwich complexes with group 15 element rings at a single metal center have remained elusive for more than 30 years. Herein, we report that the readily accessible Zintl ion E73– (E...

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Inorganic Cobalt Sandwich Complex [(η5-P5)Co(η3-P3)]−

Sandwich compounds are foundational to organometallic chemistry, yet carbon-free analogs remain exceptionally rare. We report the all-phosphorus heteroleptic cobalt sandwich anion [(η5-P5)Co(η3-P3)]− ...

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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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