93129-69-2Relevant articles and documents
Radical Anions of Aromatic Carbonitriles as Reagents for Arylation of Fluorinated Benzonitriles
Peshkov, Roman Yu.,Wang, Chunyan,Panteleeva, Elena V.,Rybalova, Tatyana V.,Tretyakov, Evgeny V.
, (2019/01/21)
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.
Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids
Kan, Jian,Huang, Shijun,Lin, Jin,Zhang, Min,Su, Weiping
supporting information, p. 2199 - 2203 (2015/02/19)
A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.
A novel and convenient synthesis of benzonitriles: Electrophilic cyanation of aryl and heteroaryl bromides
Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
supporting information; experimental part, p. 4217 - 4222 (2011/05/06)
N-Cyano-N-phenyl-p-methylbenzenesulfonamide has been used as a more benign electrophilic cyanation reagent for the synthesis of various benzonitriles from (hetero)aryl bromides via formation of Grignard reagents. Electronically different and sterically demanding aryl bromides including functionalized substrates and heteroaryl bromides are successfully cyanated in good to excellent yields. The efficiency of the present methodology is shown by the expeditious syntheses of interesting pharmaceutical intermediates. Notably, chemoselective monocyanation of dibromoarenes is also achieved. Copyright
