Synthesis of 2-X-, 3-X-4,4 '-Dicyanobiphenyls (X = CH3, OCH3, F) by Cross-Coupling of the Terephthalonitrile Dianion with Substituted Benzonitriles

Synthesis of 2-X-, 3-X-4,4 '-Dicyanobiphenyls (X = CH3, OCH3, F) by Cross-Coupling of the Terephthalonitrile Dianion with Substituted Benzonitriles Full article

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Output data

Year: 2015, Volume: 2015, Number: 20, Pages: 4524-4531 Pages count : 8 DOI: 10.1002/ejoc.201500295

Tags

Cross-coupling; Electron transfer; Nucleophilic substitution; Reactive intermediates; Biaryls

Authors

Peshkov Roman Yu. ^1,2 , Panteleeva Elena V. ^1,2 , Shchegoleva Lyudmila N. ¹ , Bagryanskaya Irina Yu. ^1,2 , Rybalova Tatyana V. ^1,2 , Vasilieva Nadezhda V. ¹ , Shteingarts Vitalij D. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia

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.

Peshkov R.Y. , Panteleeva E.V. , Shchegoleva L.N. , Bagryanskaya I.Y. , Rybalova T.V. , Vasilieva N.V. , Shteingarts V.D.
Synthesis of 2-X-, 3-X-4,4 '-Dicyanobiphenyls (X = CH3, OCH3, F) by Cross-Coupling of the Terephthalonitrile Dianion with Substituted Benzonitriles
European Journal of Organic Chemistry. 2015. V.2015. N20. P.4524-4531. DOI: 10.1002/ejoc.201500295 WOS Scopus РИНЦ

Published online:	Jun 10, 2015
Published print:	Jul 1, 2015

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