Overcoming Challenges in O‐Nitration: Selective Alcohol Nitration Deploying N,6‐Dinitrosaccharin and Lewis Acid Catalysis DOI Creative Commons
Anthony J. Fernandes,

Vasiliki Valsamidou,

Dmitry Katayev

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: July 10, 2024

Abstract 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 nitrates via direct O ‐nitration alcohols, addressing limitations current traditional methods. Leveraging bench‐stable recoverable N ,6‐dinitrosaccharin reagent, our strategy employs magnesium triflate to achieve mild selective offering broad substrate scope unprecedentedly large functional group tolerance (e.g. alkenes, alkynes, carbonyls). DFT mechanistic studies reveal dual role catalyst activation both nitrating reagent alcohol substrate. They also unveil barrierless proton transfer upon formation widely‐accepted – yet elusive solution nitrooxonium ion intermediate. Overall, work contributes mild, selective, sustainable approaches synthesis, with potential applications drug discovery, materials science, environmental chemistry.

Language: Английский

Mechanochemistry Drives Alkene Difunctionalization via Radical Ligand Transfer and Electron Catalysis DOI Creative Commons
Subrata Patra,

Bhargav N. Nandasana,

Vasiliki Valsamidou

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(29)

Published: June 3, 2024

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

Language: Английский

Citations

6
Overcoming High Reduction Potentials via Consecutive Mechanical-Force-Induced Electron Transfer Strategy DOI Creative Commons
Zhong Lian, Xiaohong Wang, X. He

et al.

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Abstract Mechanical-force-induced redox catalysis has recently advanced rapidly, emerging as a green and innovative tool in synthetic chemistry. The foundation of this strategy lies the single electron transfer (SET) from polarized piezoelectric materials to substrates, which is initiated by potential generated through mechanical agitation. magnitude primarily influenced intrinsic properties material. In certain circumstances, however, may be insufficient trigger SET process, akin limitations visible-light excitation photocatalytic reactions. This challenge motivated us explore effective solutions. work, we establish catalytic system that utilizes consecutive mechanical-force-induced (ConMET) strategy. novel employs mechanochemical catalysts, with 9-phenyl-dihydroacridine (D1) serving sacrificial donors, facilitating produce significantly more powerful reductive species during grinding. Our approach effectively promotes reduction aryl iodides, bromides even electron-rich chlorides, possess potentials high − 2.8 V (vs. SCE), leading formation radicals. Ultimately, enables anti-Markovnikov hydroarylation alkenes dehalogenative deuteration aromatic halides (Cl, Br) under mild conditions.

Language: Английский

Citations

0
Mechanochemical Sequential Deoxygenative Cross-Coupling Reactions of Phenols Under Ruthenium-Nickel Catalysis DOI Creative Commons
Satenik Mkrtchyan, Vishal B. Purohit, Michał Jakubczyk

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(8), P. 1835 - 1835

Published: April 19, 2025

Herein, we report the first mechanochemical strategy for Ru-catalyzed deoxygenative borylation of free phenols via C–O bond cleavage. This phenolic approach has been successfully extended to Suzuki–Miyaura-type cross-coupling with aryl bromides. The protocol accepts a wide scope substrates, allowing synthesis pinacolboranes and biphenyl structures in excellent yields serving as better alternative classical reactions context pot, atom, step economy synthesis.

Language: Английский

Citations

0
Merging Iron-Mediated Radical Ligand Transfer (RLT) Catalysis and Mechanochemistry for Facile Dihalogenation of Alkenes DOI
Subrata Patra,

Vasiliki Valsamidou,

Bhargav N. Nandasana

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 13747 - 13758

Published: Aug. 30, 2024

With the growing emphasis on cost- and atom-economical chemical synthesis, mechanochemistry has attracted considerable attention for providing environmentally friendly alternatives to traditional solvent-based organic transformations. Herein, we demonstrate use of facilitate alkene dihalogenation via iron-mediated radical ligand transfer (RLT) catalysis, producing diverse vicinal dichloro, dibromo, bromochloro molecules. The method is characterized by its simplicity, rapid reaction time, high chemo- regioselectivity, broad functional group tolerance, accommodating both activated unactivated alkenes alkynes. Mechanistic insights suggest nature these processes, underscoring effectiveness mechanochemically driven RLT catalysis modular functionalization unsaturated hydrocarbons.

Language: Английский

Citations

3
Overcoming Challenges in O‐Nitration: Selective Alcohol Nitration Deploying N,6‐Dinitrosaccharin and Lewis Acid Catalysis DOI Creative Commons
Anthony J. Fernandes,

Vasiliki Valsamidou,

Dmitry Katayev

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 23, 2024

Abstract 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 nitrates via direct O ‐nitration alcohols, addressing limitations current traditional methods. Leveraging bench‐stable recoverable N ,6‐dinitrosaccharin reagent, our strategy employs magnesium triflate to achieve mild selective offering broad substrate scope unprecedentedly large functional group tolerance (e.g. alkenes, alkynes, carbonyls). DFT mechanistic studies reveal dual role catalyst activation both nitrating reagent alcohol substrate. They also unveil barrierless proton transfer upon formation widely‐accepted – yet elusive solution nitrooxonium ion intermediate. Overall, work contributes mild, selective, sustainable approaches synthesis, with potential applications drug discovery, materials science, environmental chemistry.

Language: Английский

Citations

1
Overcoming Challenges in O‐Nitration: Selective Alcohol Nitration Deploying N,6‐Dinitrosaccharin and Lewis Acid Catalysis DOI Creative Commons
Anthony J. Fernandes,

Vasiliki Valsamidou,

Dmitry Katayev

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: July 10, 2024

Abstract 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 nitrates via direct O ‐nitration alcohols, addressing limitations current traditional methods. Leveraging bench‐stable recoverable N ,6‐dinitrosaccharin reagent, our strategy employs magnesium triflate to achieve mild selective offering broad substrate scope unprecedentedly large functional group tolerance (e.g. alkenes, alkynes, carbonyls). DFT mechanistic studies reveal dual role catalyst activation both nitrating reagent alcohol substrate. They also unveil barrierless proton transfer upon formation widely‐accepted – yet elusive solution nitrooxonium ion intermediate. Overall, work contributes mild, selective, sustainable approaches synthesis, with potential applications drug discovery, materials science, environmental chemistry.

Language: Английский

Citations

0