Oxidative alkylamination of aromatic and heteroaromatic substrates and accompanying heterocyclization reactions

Gulevskaya, A. V.; Пожарский, А. Ф.

doi:10.1007/s11172-008-0127-3

Cited by 13 publications

(1 citation statement)

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“…Procedures that do not require such preactivation of substrate and can be carried out at ambient temperature are therefore highly attractive. The oxidative alkylamination, via oxidative nucleophilic aromatic substitution of hydrogen (ONSH), pioneered by H. van der Plas, offers such an alternative since no leaving group is required . The oxidative alkylamination is considered to involve a two-step mechanism: σ Η -adduct formation followed by oxidative rearomatization.…”

Section: Introductionmentioning

confidence: 99%

ONSH: Optimization of Oxidative Alkylamination Reactions through Study of the Reaction Mechanism

Verbeeck

Herrebout²,

Gulevskaya

et al. 2010

J. Org. Chem.

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Oxidative alkylamination of electron-deficient (hetero)aromatic compounds, via the nucleophilic substitution of hydrogen, is a methodology that has made significant progress since the introduction of AgPy(2)MnO(4) as oxidant. This oxidant generally gives good conversions and yields, whereas the use of KMnO(4) only sometimes works equally well. In order to rationalize this, the reaction mechanism of oxidative alkylamination has been studied. 3-Nitropyridine (1), 1,3-dinitrobenzene (2), and quinazoline (3) were chosen as model substrates and n-butylamine and pyrrolidine as model alkylamines. The rate-limiting step of the mechanism for these substrate/alkylamine combinations was determined. With the use of (1)H NMR spectroscopy thermodynamic properties of sigma(Eta)-adduct formation were deduced and the effect of additives on the adduct formation was investigated. The fundamental insights resulting from these studies led to the identification of a cheap additive (tetrabutylammonium chloride), which in combination with the standard and cheap oxidant KMnO(4) generally gave excellent yields, similar to the ones previously obtained with more expensive AgPy(2)MnO(4).

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Section: Introductionmentioning

confidence: 99%

ONSH: Optimization of Oxidative Alkylamination Reactions through Study of the Reaction Mechanism

Verbeeck

Herrebout²,

Gulevskaya

et al. 2010

J. Org. Chem.

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Nucleophilic Aromatic Substitution

Crampton

2015

Arene Chemistry

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Symmetry‐Broken Intermolecular Charge Separation of Cationic Radicals

et al. 2023

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A quadrupolar compound Pyr‐BA with two pyrrole‐type nitrogen atoms doped externally was prepared in this work. In high contrast with other π ionic radicals, its cationic radical Pyr‐BA⋅+ undergoes unusual symmetry‐broken charge separation (SB‐CS), generating the mixed valence complex of Pyr‐BA+1−q⋅⋅⋅Pyr‐BA+1+q, where q is the degree of charge transfer. Variable‐temperature (VT) single‐crystal analysis, absorption and EPR experiments all confirmed that aggregation and lower temperature would help to facilitate this SB‐CS process. Gibbs energy calculations and gauge‐including magnetically induced current simulation both validate that, for Pyr‐BA⋅+, SB‐CS behavior is more favorable than the conventional dimerization mode. To the best of our knowledge, this is the first study that shows solid single‐crystal evidence for spontaneous SB‐CS between identical ionic radicals. Such a unique phenomenon is of great significance both in terms of fundamental aspects and uncharted material science.

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Oxidative alkylamination of aromatic and heteroaromatic substrates and accompanying heterocyclization reactions

Cited by 13 publications

References 43 publications

ONSH: Optimization of Oxidative Alkylamination Reactions through Study of the Reaction Mechanism

ONSH: Optimization of Oxidative Alkylamination Reactions through Study of the Reaction Mechanism

Nucleophilic Aromatic Substitution

Symmetry‐Broken Intermolecular Charge Separation of Cationic Radicals

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