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Synthesis of 2‐X‐, 3‐X‐4,4′‐Dicyanobiphenyls (X = CH 3 , OCH 3 , F) by Cross‐Coupling of the Terephthalonitrile Dianion with Substituted Benzonitriles
Author(s) -
Peshkov Roman Yu.,
Panteleeva Elena V.,
Shchegoleva Lyudmila N.,
Bagryanskaya Irina Yu.,
Rybalova Tatyana V.,
Vasilieva Nadezhda V.,
Shteingarts Vitalij D.
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500295
Subject(s) - chemistry , benzonitrile , heterolysis , regioselectivity , reagent , computational chemistry , stereochemistry , medicinal chemistry , organic chemistry , catalysis
A concise noncatalytic synthetic approach to 2‐ and 3‐substituted 4,4′‐dicyanobiphenyls by applying terephthalonitrile dianion 1 2– as para ‐cyanophenylating reagent for neutral benzonitriles is described. Neutral participants are varied to reveal the scope of applicable substrates and to evaluate the electronic and structural factors governing the regioselectivity and efficiency of the cross‐coupling. Benzonitriles substituted with Me, OMe and F provide the corresponding dicyanobiphenyls in good yields. The regularities in the reactivities are interpreted in terms of a reaction scheme involving the intermediacy of a charge‐transfer complex between 1 2– and benzonitrile, which transforms into a dimeric dianion either through a heterolytic pathway and/or by successive single electron transfer and recombination of the primary generated radical anions. Quantum chemical calculations of the structure and energy of the principal reaction intermediates match the experimental data. CV measurements of the new dicyanobiphenyls are also included.