Reactions of oxidative nucleophilic substitution of hydrogen in nitroarenes

Gulevskaya, A. V.; Tyaglivaya, I. N.

doi:10.1007/s11172-012-0178-3

Cited by 12 publications

(3 citation statements)

References 49 publications

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“…28 Table 7 outlines the extension of ketene N,O-acetal synthesis to intermolecular reactions between α-pyridinyl carbanions and monoperoxyacetals. Following metal−halogen exchange, lithiated pyridine consumed primary, peroxide anticipated, the addition of a nitro group to the pyridine system activated the heterocycle toward nucleophilic aromatic substitution, 33 leaving a large amount of the peroxide starting material unreacted. Efforts to react an α-heteroaryl carbanion, bearing an electron-donating substituent in the β (or 3)-position, with monoperoxyacetals were unsuccessful (Scheme 2).…”

Section: ■ Resultsmentioning

confidence: 99%

“…Similar to that observed with indole molecules, pyridine substrates bearing an electron-withdrawing group (NO 2 ) in position 3 or position 4 failed to react with a monoperoxyacetal (Table , 28a , 28b ). As anticipated, the addition of a nitro group to the pyridine system activated the heterocycle toward nucleophilic aromatic substitution, leaving a large amount of the peroxide starting material unreacted.…”

Section: Resultsmentioning

confidence: 99%

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Electrophilic Etherification of α-Heteroaryl Carbanions with Monoperoxyacetals as a Route to Ketene O,O- and N,O-Acetals

2021

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Alkyl ketene acetals are useful reactants in a variety of synthetic processes, and yet, there are limited routes to their formation as isolable products. We now report the successful synthesis and isolation of heteroaryl ketene acetals through intermolecular transfer of alkoxyl (δ + OR) from electrophilic peroxides to lithiated benzofurans, indoles, and pyridines. Primary and secondary peroxyacetals enable selective transfer of the nonanomeric alkoxy group in moderate to high yield; substrates bearing an electron-donating substituent show enhanced reactivity toward electrophilic oxygen. Heteroaryl ketene acetals are remarkably stable throughout traditional purification techniques; the superior stability of ketene N,O-acetals compared to ketene O,O-acetals is presumably due to increased aromaticity of the indole and pyridine structures. The presented method overcomes typical problems associated with alkyl ketene acetal synthesis as reported products withstood workup and flash column chromatography procedures.

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Section: ■ Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Electrophilic Etherification of α-Heteroaryl Carbanions with Monoperoxyacetals as a Route to Ketene O,O- and N,O-Acetals

2021

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“…On the basis of static gas-phase calculations on various halobenzenes and halonitrobenzenes, Glukhovtsev et al suggested a one-step or stepwise mechanism depending on the halide and on the number of activating nitro groups on the ring . It should be mentioned that besides the S N Ar reaction, which typically involves the substitution of a halogen atom, a competing hydrogen substitution may occur through the S N ArH reaction, − which involves the σ H addition of a nucleophile at an unsubstituted position, followed by hydrogen elimination through various reaction pathways.…”

Section: Introductionmentioning

confidence: 99%

Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia

et al. 2016

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The role of the solvent and the influence of dynamics on the kinetics and mechanism of the SNAr reaction of several halonitrobenzenes in liquid ammonia, using both static calculations and dynamic ab initio molecular dynamics simulations, are investigated. A combination of metadynamics and committor analysis methods reveals how this reaction can change from a concerted, one-step mechanism in gas phase to a stepwise pathway, involving a metastable Meisenheimer complex, in liquid ammonia. This clearly establishes, among others, the important role of the solvent and highlights the fact that accurately treating solvation is of crucial importance to correctly unravel the reaction mechanism. It is indeed shown that H-bond formation of the reacting NH3 with the solvent drastically reduces the barrier of NH3 addition. The halide elimination step, however, is greatly facilitated by proton transfer from the reacting NH3 to the solvent. Furthermore, the free energy surface strongly depends on the halide substituent and the number of electron-withdrawing nitro substituents.

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Aerobic Transition‐Metal‐Free Synthesis of 2,3‐Diarylindoles and 5‐Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

Moon

Kim

et al. 2015

Bulletin Korean Chem Soc

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Reactions of oxidative nucleophilic substitution of hydrogen in nitroarenes

Cited by 12 publications

References 49 publications

Electrophilic Etherification of α-Heteroaryl Carbanions with Monoperoxyacetals as a Route to Ketene O,O- and N,O-Acetals

Electrophilic Etherification of α-Heteroaryl Carbanions with Monoperoxyacetals as a Route to Ketene O,O- and N,O-Acetals

Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia

Aerobic Transition‐Metal‐Free Synthesis of 2,3‐Diarylindoles and 5‐Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

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