24309-22-6Relevant articles and documents
Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
Reeves, Jonathan T.,Malapit, Christian A.,Buono, Frederic G.,Sidhu, Kanwar P.,Marsini, Maurice A.,Sader, C. Avery,Fandrick, Keith R.,Busacca, Carl A.,Senanayake, Chris H.
supporting information, p. 9481 - 9488 (2015/08/11)
An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. (Chemical Equation Presented).
A state-of-the-art cyanation of aryl bromides: A novel and versatile copper catalyst system inspired by nature
Schareina, Thomas,Zapf, Alexander,Maegerlein, Wolfgang,Mueller, Nikolaus,Beller, Matthias
, p. 6249 - 6254 (2008/02/13)
A general protocol for the cyanation of aryl halides with the nontoxic cyanide source K4[Fe(CN)6] using copper catalysis and a ligand system based on 1-alkylimidazoles is presented. The advantages of this system are the high selectivity, a unique substrate range, easy handling, and inexpensive reagents.
Anodic Cyanation of tert-Butylated Anisoles: Competitive Aromatic Additions and Substitutions
Yoshida, Kunihisa,Takeda, Kazusada,Fueno, Takayuki
, p. 3095 - 3098 (2007/10/02)
The electrooxidation of sevral tert-butylated anisoles has been carried out in ,ethanol containing sodium cyanide at a Pt anode in a divided cell.Two types of reactions occured competitively, aromatic-ring addition and substitution.Increasing the level of tert-butyl substitution raises the relative extent of addition to the aromatic ring.An MO calculation has indicated that the order of orientational preference for substitution of the aromatic hydrogen of alkylanisole cation radicals is explained in terms of the LUMO electron densities calculated for the cation radicals.The effect of structure on the oxidation potential of alkylanisoles has also been studied. para Substitution lowers the oxidation potential while ortho substitution raises the potential.