Anionic reduced forms of electron-deficient arenes in reactions with C–C bond formation

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

“…In order to expand the scope of the synthetic utilization of the cross-coupling reaction under investigation, as well as to work out a short and convenient approach to a number of universal carbonitrilic structural blocks with different both aryl and alkyl moieties [ 16 – 19 ], we varied the nature of the neutral participant 2 in the coupling with dianion 1 2 – and also the reagent for anion 3 alkylation. The presented results not only support the approach based on anionic forms of cyanoarenes as effective cross-coupling reagents toward neutral unactivated substrates [ 26 – 27 ], but also expand the knowledge about nucleophilic mechanisms such as aromatic substitution of a hydrogen atom (S N H) [ 28 ] and the vicarious substitution [ 29 ].…”

Structural characterization and bonding properties of lithium naphthalene radical anion, [Li+(TMEDA)2][C10H8˙−], and lithium naphthalene dianion [(Li+TMEDA)2C10H8−2]

“…Indeed, the investigation of new patterns of reactivity in anionic polycyclic aromatic hydrocarbons having occupied orbitals of very high energy is affording exciting results, both from the fundamental point of view of reactivity (e.g. transition from ET to S N 2), 11, 12 as well as from a more practical point of view regarding new synthetic pathways (e.g. reaction with propene, which carbolithiation is exclusive of arene dianions).…”