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

Synthesis of Primary and Secondary Amines via Electrochemical Reduction of Hydrazines DOI

Dong Wang,

Qiulu Wang,

Mingxia Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(51), P. 11123 - 11128

Published: Dec. 13, 2024

We herein introduce an electrochemical route for the N–N bond cleavage of hydrazines. This mild and green methodology utilized readily available mono- 1,1-disubstituted hydrazines or their HCl salts as starting materials to access a broad scope primary secondary amines in high yields. The mechanistic investigation suggests that amine product is formed by consecutive SET reduction, utilization hydrazine salt important providing sufficient conductivity acidity facilitate this reaction.

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
Photocatalyst-free Light-Mediated Three-Component Alkoxy-, Hydroxy-, and Azidotrifluoromethylation of Alkenes DOI Creative Commons
Yingmin Ji, Aida Jaafar, Carolina Gimbert‐Suriñach

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6660 - 6665

Published: Jan. 1, 2024

A photocatalyst-free method enables efficient alkene difunctionalization in CF 3 -rich organic environments using accessible starting materials. This protocol is applicable for the synthesis of alkoxy, hydroxy, and azido derivatives.

Language: Английский

Citations

1
Iridium Photoredox-Catalyzed Nitrative Difunctionalization of Alkenes DOI
Martin Oestreich, Hendrik F. T. Klare, Phillip Pommerening

et al.

Synfacts, Journal Year: 2024, Volume and Issue: 20(03), P. 0279 - 0279

Published: Feb. 14, 2024

Key words alkenes - iridium catalysis nitrative difunctionalization radical ligand transfer radical-polar crossover

Language: Английский

Citations

0
Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C–H Bonds DOI
Ravi Kumar Venkatraman, Amal Hassan Tolba, Theis I. Sølling

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(23), P. 6202 - 6208

Published: June 5, 2024

The usage of rare-earth-metal catalysts in the synthesis organic compounds is widespread chemical industries but limited owing to its environmental and economic costs. However, recent studies indicate that abundant-earth metals like iron(III) chloride can photocatalyze diverse transformations using blue-light LEDs. Still, underlying mechanism behind such activity debatable controversial, especially absence ultrafast spectroscopic results. To address this urgent challenge, we performed femtosecond time-resolved electronic absorption spectroscopy experiments selected solvents relevant photocatalytic applications. Our results show long-lived species [Fe(II) ← Cl

Language: Английский

Citations

0
Trifunctionalization of C=C Bonds in Vinyl Azides to Access Densely Functionalized Phenanthridines Enabled by the NCS/AgNO2 System DOI

Shaobo Ren,

Jian Zhu, Yunkui Liu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(29), P. 5982 - 5986

Published: Jan. 1, 2024

An unprecedented trifunctionalization of CC bonds in 2-(1-azidovinyl)-1,1'-biphenyls has been successfully achieved using the NCS/AgNO

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