Differences in reactivity of stabilized carbanions with haloarenes in the initiation and propagation steps of the SRN1 mechanism in DMSO

Borosky, Gabriela L.; Pierini, Adriana B.; Rossi, Roberto A.

doi:10.1021/jo00027a044

Cited by 43 publications

(43 citation statements)

References 4 publications

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“…The exothermicity of the reaction of Ph' with acetophe-none, 1, and acetylacetone enolate ions are calculatedt to be 70, 60, and 36 kcal/ mol, respectively, which parallels the order of reactivity determined experimentally [27].…”

Section: Solvent Effectsupporting

confidence: 64%

An AM1 study of the coupling reaction of radicals with the acetone enolate ion and some related nucleophiles

Pierini

Borosky

Baumgartner

1992

Int J of Quantum Chemistry

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We here report an AM^ study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl = bicyclo-[2.2.l]hept-l-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1, phenoxide, or phenylamide anions is also explained on a theoretical basis. Q

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Section: Solvent Effectsupporting

confidence: 64%

An AM1 study of the coupling reaction of radicals with the acetone enolate ion and some related nucleophiles

Pierini

Borosky

Baumgartner

1992

Int J of Quantum Chemistry

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“…8,9 On the other hand, phenylation as well as heteroarylation of the anion is possible in DMSO under photostimulation. 10,11 A similar behavior has been observed with the enolate ions of 2-acetylnaphthalene 12 and other aromatic ketones such as 2-acetylfuran, 11,8b and 2-acetylthio-phene. 13 The latter carbanion has been reported to afford the substitution product by reaction with phenyl azosulfides, 13 which are very good electron acceptors that react spontaneously or under laboratory light with different nucleophiles.…”

supporting

confidence: 59%

Reaction of o-Iodoaniline with Aromatic Ketones in DMSO: Synthesis of 2-Aryl or 2-Hetarylindoles

Baumgartner¹,

Nazareno²,

Murguía³

et al. 1999

Synthesis

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The reactions of o-iodoaniline (1) with the enolate anions from acetone (2), acetophenone (4), 2-acetylnaphthalene (6), 2acetyl-1-methylpyrrole (8a) and 2-acetylthiophene (8b) in DMSO give respectively the corresponding 2-substituted indoles in 63, 88, 73, 93 and 82% yields. These reactions are proposed to take place by an S RN 1 mechanism. Depending on the ketone enolate ion involved, the reactions can occur under light or Fe(II) salts initiation.

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“…0.25 V (Eqn 14); thus, a large shift of the anodic peak potential values can be observed between the neutral and the corresponding anions. For example, selenobenzamide anion (1) and thiobenzamide anion (5) show shifts of 700 and 1100 mV respectively. The cyclic voltammograms for the rest of the anions listed in Chart 1 can be found in the Supporting Information.…”

Section: Electrochemical Behaviour Of Thioamides Selenamides and Thementioning

confidence: 99%

“…When the nucleophile is not able to initiate the reaction an “entrainment” reagent is added to the reaction mixture; in most of the cases, an excess of a base like potassium tert ‐butoxide ( tert ‐BuOK) is used. Even there is a general trend between the basicity of the nucleophile and its reduction power, in most of the cases a comprehensive study including proton affinity, reducing power and photochemical behaviour is not considered. In addition, for our particular interest, very little is known about the redox properties of chalcogenide compounds.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical and computational study of the initiation step in the photoinduced electron transfer reaction between sulphur and selenide nucleophiles toward 1‐bromonaphthalene

Bouchet

Pierini

Brunetti

et al. 2016

J of Physical Organic Chem

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The initiation step of the photosubstitution reaction between 1-bromonaphthalene and a number of nucleophilic sulphur and selenium centred anions to afford 1-naphthylsulphide/selenide derivatives was investigated experimentally and by means of quantum chemical calculations. The frontier orbital energies of the anions were computed, and the values obtained agree with the lack of reactivity in the ground state. This model fails in accounting different reactivity of the anions toward the triplet state of 1-bromonaphthalene. Basicity and E ox were also calculated for all the anions finding a better agreement with the experimental reactivity and other measured properties such as pKa and oxidation potentials.

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Differences in reactivity of stabilized carbanions with haloarenes in the initiation and propagation steps of the SRN1 mechanism in DMSO

Cited by 43 publications

References 4 publications

An AM1 study of the coupling reaction of radicals with the acetone enolate ion and some related nucleophiles

An AM1 study of the coupling reaction of radicals with the acetone enolate ion and some related nucleophiles

Reaction of o-Iodoaniline with Aromatic Ketones in DMSO: Synthesis of 2-Aryl or 2-Hetarylindoles

Electrochemical and computational study of the initiation step in the photoinduced electron transfer reaction between sulphur and selenide nucleophiles toward 1‐bromonaphthalene

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