Copper‐Catalyzed Aromatic CH Bond Cyanation by CCN Bond Cleavage of Inert Acetonitrile

Abstract

Cut and paste! A Cu‐catalyzed aromatic CH cyanation with acetonitrile as the nitrile source by CCN cleavage has been developed (see scheme; TMEDA=N,N,N′,N′‐tetramethylethylenediamine). The reaction is catalytic in copper, and it is found that using (Me3Si)2 as an additive plays a critical role in promoting CCN cleavage and enhancing the reaction rate.

Ru‐Catalysed CH Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies

“…A number of groups have since described the use of this species in both the synthesis[ 24 , 26 ] and derivatisation of indoles and pyrroles by using various metals. [ 27 – 32 ]…”

Functionalization of the imidazo[1,2-a]pyridine ring in α-phosphonoacrylates and α-phosphonopropionates via microwave-assisted Mizoroki–Heck reaction

“…The second side product, compound 5, is probably the result of the cleavage of the C-CN bond in the solvent (propionitrile or acetonitrile), followed by a palladium-catalyzed cyanation of substrate 1. Recently, acetonitrile was reported as a nontoxic source of cyanide [19,20]. Having the optimized conditions in hand, the scope of this transformation was examined using selected olefins and the substrate containing imidazo[1,2-a]pyridine ring embedded either within 2-(diethoxyphosphoryl)acrylate (analogs 1) or 2-(diethoxyphosphoryl)propanoates (analogs 2).…”

Reaction Medium as the Installing Reservoir for Key Functionalities in the Molecules

“…Similarly generation of CN − anion was achieved using various systems such as Cu, NaH . Formation of metal‐cyano complexes were also observed during the cyanation and cyanomethylation using ACN with the various metals such as Ni, Ir‐PNP pincer, [70 NiNCOP Pincer, Cu, Cu/Ag and Ag . Shen and coworkers demonstrated that in presence of copper and TEMPO in a reaction, both cyanide anion as well as cyanide radical formations are possible …”