Radical Anions of Aromatic Carbonitriles as Reagents for Arylation of Fluorinated Benzonitriles

• Published in: Journal of organic chemistry 2019-01, Vol.84 (2), p.963-972
• Main Authors: Peshkov, Roman Yu, Wang, Chunyan, Panteleeva, Elena V, Rybalova, Tatyana V, Tretyakov, Evgeny V
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.8b02904

The first example of phenylation of fluorobenzonitriles with the sodium salt of a benzonitrile radical anion in liquid ammonia is presented. The reaction regioselectivity corresponds to the ortho- and para-fluorine atom substitution in fluorobenzonitrile with the phenyl moiety of the benzonitrile radical anion and affords 2- and 4-cyanobiphenyls in 40–90% yields. 3-Methoxybenzonitrile as well as 1-cyanonaphthalene radical anions were also successfully subjected to this interaction forming 3′-methoxycyanobiphenyls and (1-naphthyl)­benzonitriles, respectively. The radical anion acts as an ipso-C-nucleophile with consequent loss of the cyano group. The revealed new type of radical anion reactivity opens up the prospect of developing a general approach to fluorinated cyanobisarenes on the basis of an interaction of the cyanoarene radical anion with fluorinated substrates activated to aromatic nucleophilic substitution.