scholarly journals Gas-phase electrophilic aromatic substitution mechanism with strong electrophiles explained by ab initio non-adiabatic dynamics

2014 ◽  
Vol 16 (35) ◽  
pp. 18686-18689 ◽  
Author(s):  
Daniel Kinzel ◽  
Shmuel Zilberg ◽  
Leticia González
Keyword(s):  
Electron Transfer ◽  
Ab Initio ◽  
Gas Phase ◽  
Radical Pair ◽  
Electrophilic Aromatic Substitution ◽  
Single Electron Transfer ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Substitution Mechanism ◽  
Adiabatic Dynamics

Ultrafast single electron transfer producing a radical pair governs the formation of a σ-complex in gas-phase electrophilic aromatic substitution reactions.

Thoughts about the electrophilic aromatic substitution mechanism: the Friedel-crafts alkylation and acylation of benzene with acetyl and t-butyl cations in the gas phase

2017 ◽  
Vol 28 (2) ◽  
pp. 545-553 ◽  
Author(s):  
Fernanda G. Oliveira ◽  
Fabio L. Rodrigues ◽  
Alline V. B. de Oliveira ◽  
Daniel V. L. M. Marçal ◽  
Pierre M. Esteves
Keyword(s):  
Gas Phase ◽  
Electrophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Mechanism

Sulfonyl esters. 2. CS cleavage in some substitution reactions of nitrobenzenesulfonates

1990 ◽  
Vol 68 (8) ◽  
pp. 1450-1455 ◽  
Author(s):  
James Clayton Baum ◽  
Jimat Bolhassan ◽  
Richard Francis Langler ◽  
Paul Joseph Pujol ◽  
Raj Kumar Raheja
Keyword(s):  
Electron Transfer ◽  
Molecular Orbital ◽  
Radical Anion ◽  
Nucleophilic Aromatic Substitution ◽  
Bond Rupture ◽  
Single Electron Transfer ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Nucleophilic Aromatic Substitutions ◽  
Aromatic Sulfonate

An attempt to explore aromatic sulfonate esters as agents for the condensation of alcohols with mercaptans revealed an unusual process for sulfonate esters: CS bond rupture. Two mechanistic possibilities for CS bond rupture are explored: (i) radical anion intermediacy via single electron transfer and (ii) nucleophilic aromatic substitution. Both experiments and molecular orbital computations are presented to support the conclusion that nucleophilic aromatic substitutions are occurring. Keywords: sulfonyl esters, nitrobenzenesulfonates, CS bond rupture.

scholarly journals Evidence of single electron transfer from the enolate anion of an N,N′-dialkyldiketopiperazine additive in BHAS coupling reactions

2017 ◽  
Vol 15 (41) ◽  
pp. 8810-8819 ◽  
Author(s):  
Katie J. Emery ◽  
Tell Tuttle ◽  
John A. Murphy
Keyword(s):  
Electron Transfer ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Coupling Reactions ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Homolytic Aromatic Substitution ◽  
Enolate Anion

A designed N,N′-dialkyldiketopiperazine (DKP) provides evidence for the role of DKP additives as initiators that act by electron transfer in base-induced homolytic aromatic substitution reactions, involving coupling of haloarenes to arenes.

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