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
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
Synergistic Synthesis and Computational Analysis of Novel Indazole-2-Pyrone Hybrids: Toxicity, Hirshfeld Surface Insights, and Antiviral Potential against HIV-1 and Coronaviruses DOI
Mohamed El Ghozlani, Yassine Hakmaoui, Abdellatif Rafik

et al.

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1321, P. 139900 - 139900

Published: Sept. 8, 2024

Language: Английский

Citations

2
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
Utilizing NCP@PO(OH)2 as a Core-Shell Magnetic Nano-Catalyst for the Conversion of β-Hydroxy Nitrile to α,β-Unsaturated Carboxylic Acid DOI
Farzaneh Ebrahimzadeh

Letters in Organic Chemistry, Journal Year: 2024, Volume and Issue: 22(1), P. 70 - 77

Published: May 30, 2024

The synthesis of &#945;,&#946;-unsaturated compounds is crucial in organic chemistry, especially drug discovery and pharmaceutical development. In this study, NCP@POCl<sub>2</sub>-x (Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@ chitosan@POCl<sub>2</sub>-x) has been introduced as a new, environmentally friendly, highly efficient heterogeneous magnetic nanocatalyst for the carboxylic acids. This catalyst facilitates <i>in situ</i> transformation POCl<sub>2</sub>-x to PO(OH)<sub>2</sub> presence water, effectively converting &#946;-hydroxy nitriles into acids through specific mechanism involving water heat. reactions display notable regioselectivity, leading high-purity products quantitative yields. NCP@PO(OH)<sub>2</sub> exhibits heterogeneity, properties, straightforward recovery, outstanding performance, making it valuable selective transformations nitriles. Additionally, can be easily separated from mixture using external forces.

Language: Английский

Citations

0
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