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

Alkene dialkylation by triple radical sorting DOI
Johnny Wang, William L. Lyon, David W. C. MacMillan

et al.

Nature, Journal Year: 2024, Volume and Issue: 628(8006), P. 104 - 109

Published: Feb. 13, 2024

Language: Английский

Citations

39
Asymmetric Cross-Coupling of Aldehydes with Diverse Carbonyl or Iminyl Compounds by Photoredox-Mediated Cobalt Catalysis DOI

Zhiyong Chi,

Jia-Bin Liao,

Xiuliang Cheng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10857 - 10867

Published: April 8, 2024

The asymmetric cross-coupling of unsaturated bonds, hampered by their comparable polarity and reactivity, as well the scarcity efficient catalytic systems capable diastereo- enantiocontrol, presents a significant hurdle in organic synthesis. In this study, we introduce highly adaptable photochemical cobalt catalysis framework that facilitates chemo- stereoselective reductive cross-couplings between common aldehydes with broad array carbonyl iminyl compounds, including N-acylhydrazones, aryl ketones, aldehydes, α-keto esters. Our methodology hinges on synergistic mechanism driven photoredox-induced single-electron reduction subsequent radical–radical coupling, all precisely guided chiral catalyst. Various optically enriched β-amino alcohols unsymmetrical 1,2-diol derivatives (80 examples) have been synthesized good yields (up to 90% yield) high stereoselectivities >20:1 dr, 99% ee). Of particular note, approach accomplishes unattainable transformations disparate partners without reliance any external photosensitizer, thereby further emphasizing its versatility cost-efficiency.

Language: Английский

Citations

17
Simplifying Nitration Chemistry with Bench-stable Organic Nitrating Reagents DOI Creative Commons
Subrata Patra,

Vasiliki Valsamidou,

Dmitry Katayev

et al.

CHIMIA International Journal for Chemistry, Journal Year: 2024, Volume and Issue: 78(1/2), P. 32 - 39

Published: Feb. 28, 2024

Nitro compounds play a crucial role in academia and industries, serving as building blocks for the synthesis of drugs, agrochemicals, materials. Nitration, fundamental process organic synthesis, has undergone significant evolution since 19th century. While electrophilic nitration dominates historically, recent decades have seen focus on new reagents their reactivity modes achieving mild robust nitro compounds. Our group longstanding interest developing cost-effective, readily available, recyclable nitrating derived from scaffolds. These serve controllable source nitryl radical nitronium ion species, enabling practical hydrocarbons with exceptional functional tolerance. This account details development diverse applications catalytic across various classes molecules.

Language: Английский

Citations

6
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
Selective Arene Photonitration via Iron-Complex β-Homolysis DOI Creative Commons

Shuyang Liu,

Ziyu Gan, Min Jiang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(12), P. 4899 - 4909

Published: Nov. 21, 2024

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields pharmaceuticals, dyes, pesticides, functional materials, fertilizers, explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge fumes waste acids, poor group tolerance, tremendous purification difficulty, renders mild, efficient, environmentally friendly a formidable challenge. Herein, we develop visible-light-driven biocompatible arene C–H strategy with good efficiency regioselectivity, marvelous substrate applicability wide application scale-up synthesis, total late-stage functionalization. A nitryl radical delivered through unusual β-homolysis photoexcited ferric-nitrate complex proposed to be key nitrification reagent this system.

Language: Английский

Citations

6
Radical-polar Crossover Reaction of Glycine Derivatives DOI

Youwan Ye,

Xin Zhang,

Peng Kong

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(75), P. 10378 - 10381

Published: Jan. 1, 2024

Here we report a visible-light facilitated radical addition strategy for the preparation of various natural or unnatural α-amino acids from readily available glycine derivatives and alkenes. A key aspect in achieving this side carbon chain introduction reaction, while circumventing well-documented cyclization pathway, was employment radical-polar crossover under redox neutral conditions.

Language: Английский

Citations

5
Visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes to access α, β-unsaturated ketones DOI

Xun Yang,

Yuxuan Xiao, Ying Yin

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A general method for accessing α,β-unsaturated ketones through visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes has been developed.

Language: Английский

Citations

0
Direct Synthesis of 2-Hydroxytrifluoroethylacetophenones via Organophotoredox-Mediated Net-Neutral Radical/Polar Crossover DOI Creative Commons
Albert Gallego‐Gamo, Pau Sarró, Yingmin Ji

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11682 - 11692

Published: Aug. 1, 2024

Alkene difunctionalization is a very attractive tool in synthetic organic chemistry. Herein, we disclose an operationally and practically simple method to access 2-hydroxytrifluoroethylacetophenones from styrene derivatives via photoredox catalysis. This light-mediated transformation promotes the generation of 1-hydroxy-2,2,2-trifluoroethyl carbon-centered radical as key synthon, which undergoes Giese addition with styrenes followed by Kornblum oxidation process. The presented not only mild cost-effective, but also utilizes photocatalyst DMSO oxidant. Experimental investigations support operative mechanism net-neutral radical/polar crossover.

Language: Английский

Citations

3
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
Visible-Light-Mediated Vicinal Dihalogenation of Unsaturated C–C Bonds Using Dual-Functional Group Transfer Reagents DOI Creative Commons
Rahul Giri, Egor S. Zhilin,

Mathias Kissling

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31547 - 31559

Published: Nov. 5, 2024

The growing demand for chemical production continues to drive the development of sustainable and efficient methods introducing molecular complexity. In this context, exploration unconventional functional group transfer reagents (FGTRs) has led significant advancements in practical atom-efficient synthetic protocols. Aiming advance field valuable organic synthesis, herein we report successful carbon-based, bench-stable, modular, inexpensive implemented dual halogen unsaturated hydrocarbons via photocatalytic activation based on a radical-polar crossover mechanism. This method beneficially enables vicinal dichlorination, dibromination, bromo-chlorination reactions olefins, offering alternatives use toxic binary halogens. Detailed mechanistic studies, combining experimental, spectroscopic, theoretical investigations, revealed distinctive single-electron reduction FGTR. process triggers mesolytic carbon–halogen bond cleavage, followed by radical 1,2-halide rearrangement, leading continuous generation dihalogen species reaction medium. wide applicability developed protocol is demonstrated through an extensive scope molecules, including additional operations strain-release dihalogenation.

Language: Английский

Citations

2