Nitrative Difunctionalization of Alkenes via Cobalt-Mediated Radical Ligand Transfer and Radical-Polar Crossover Photoredox Catalysis

Patra, Subrata; Giri, Rahul; Katayev, Dmitry

doi:10.1021/acscatal.3c04899

ACS Catal.

2023

DOI: 10.1021/acscatal.3c04899

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Nitrative Difunctionalization of Alkenes via Cobalt-Mediated Radical Ligand Transfer and Radical-Polar Crossover Photoredox Catalysis

Subrata Patra,

Rahul Giri,

Dmitry Katayev

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2024

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Cited by 17 publications

(1 citation statement)

References 157 publications

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“…Hence, photocatalysis by simple 3d transition metal–halogen salts has recently attracted much attention in organic synthesis/transformation. ,,− Specifically, the use of simple iron(III) chloride in selective C(sp 3 )–H activation of aliphatic alkanes, benzylic group, for oxidation, , alkylation, , borylation, phosphorylation, and azidation of alkenes, , oxidative C–C bond cleavage, , and more. − Furthermore, photocatalysis by iron(III) chloride plays a crucial role in upcycling of polystyrene , and reducing the greenhouse gases methane and tropospheric ozone. , …”

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confidence: 99%

Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C–H Bonds

Venkatraman,

Tolba,

Sølling

et al. 2024

J. Phys. Chem. Lett.

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The usage of rare-earth-metal catalysts in the synthesis of organic compounds is widespread in chemical industries but is limited owing to its environmental and economic costs. However, recent studies indicate that abundant-earth metals like iron(III) chloride can photocatalyze diverse organic transformations using blue-light LEDs. Still, the underlying mechanism behind such activity is debatable and controversial, especially in the absence of ultrafast spectroscopic results. To address this urgent challenge, we performed femtosecond time-resolved electronic absorption spectroscopy experiments of iron(III) chloride in selected organic solvents relevant to its photocatalytic applications. Our results show that the long-lived species [Fe(II) ← Cl • ]* is primarily responsible for both oxidizing the organic substrate and reducing molecular oxygen through the diffusion process, leading to the final product and regenerating the photocatalyst rather than the most widely proposed free chloride radical (Cl • ). Our study will guide the rational design of efficient earth-abundant photocatalysts.

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mentioning

confidence: 99%

Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C–H Bonds

Venkatraman,

Tolba,

Sølling

et al. 2024

J. Phys. Chem. Lett.

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Mechanochemistry Drives Alkene Difunctionalization via Radical Ligand Transfer and Electron Catalysis

Patra,

Nandasana,

Valsamidou

et al. 2024

Advanced Science

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A general and modular protocol is reported for olefin difunctionalization through mechanochemistry, facilitated by cooperative radical ligand transfer (RLT) and electron catalysis. Utilizing mechanochemical force and catalytic amounts of 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO), ferric nitrate can leverage nitryl radicals, transfer nitrooxy‐functional group via RLT, and mediate an electron catalysis cycle under room temperature. A diverse range of activated and unactivated alkenes exhibited chemo‐ and regioselective 1,2‐nitronitrooxylation under solvent‐free or solvent‐less conditions, showcasing excellent functional group tolerance. Mechanistic studies indicated a significant impact of mechanochemistry and highlighted the radical nature of this nitrative difunctionalization process.

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Overcoming Challenges in O‐Nitration: Selective Alcohol Nitration Deploying N,6‐Dinitrosaccharin and Lewis Acid Catalysis

Fernandes,

Valsamidou,

Katayev

2024

Angewandte Chemie

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Nitrate esters hold pivotal roles in pharmaceuticals, energetic materials, and atmospheric processes, motivating the development of efficient synthesis routes. Here, we present a novel catalytic method for the synthesis of nitrates via the direct O‐nitration of alcohols, addressing limitations of current traditional methods. Leveraging bench‐stable and recoverable N,6‐dinitrosaccharin reagent, our catalytic strategy employs magnesium triflate to achieve mild and selective O‐nitration of alcohols, offering broad substrate scope and unprecedented large functional group tolerance (e.g. alkenes, alkynes, carbonyls). DFT mechanistic studies reveal a dual role of the magnesium catalyst in the activation of both the nitrating reagent and the alcohol substrate. They also unveil a barrierless proton transfer upon formation of a widely‐accepted — yet elusive in solution — nitrooxonium ion intermediate. Overall, our work contributes to the development of mild, selective, and sustainable approaches to nitrates synthesis, with potential applications in drug discovery, materials science, and environmental chemistry.

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Nitrative Difunctionalization of Alkenes via Cobalt-Mediated Radical Ligand Transfer and Radical-Polar Crossover Photoredox Catalysis

Cited by 17 publications

References 157 publications

Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C–H Bonds

Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C–H Bonds

Mechanochemistry Drives Alkene Difunctionalization via Radical Ligand Transfer and Electron Catalysis

Overcoming Challenges in O‐Nitration: Selective Alcohol Nitration Deploying N,6‐Dinitrosaccharin and Lewis Acid Catalysis

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