One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Main Authors: Roman Yu. Peshkov, Elena V. Panteleeva, Wang Chunyan, Evgeny V. Tretyakov, Vitalij D. Shteingarts
• Format: Article
• Language: English
• Published: Beilstein-Institut 2016-07-01
• Series: Beilstein Journal of Organic Chemistry
• Subjects: alkylcyanobiaryls; cross-coupling; cyanoarenes; reactive intermediates; reductive alkylation
• Online Access: https://doi.org/10.3762/bjoc.12.153
• ISSN: 1860-5397

A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents.