Palladium-catalyzed cyanation of porphyrins utilizing cyanoethylzinc bromide as an efficient cyanide ion source

Palladium-catalyzed cyanation of bromoporphyrins is now realized using cyanoethylzinc bromide as a specific cyanating agent. This new protocol provides an easy access to various cyanated Zn(II) porphyrins, including meso-mono-, meso-di-, and beta-mono-cyano-substituted Zn(II) complexes. [reaction: see text]     

Copper-catalyzed cyanation of arenes using benzyl nitrile as a cyanide anion surrogate

The copper-catalyzed cyanation of arenes using benzyl nitrile as a cyanide anion surrogate furnishes aromatic nitriles in moderate to good yields. The cascade process involves a copper-catalyzed aerobic C-H oxidation, a retro-cyanohydrination, and a copper-catalyzed aerobic oxidative C-H functionalization.     

Copper-mediated cyanation of aryl halide with the combined cyanide source

A simple copper-mediated cyanation of aryl halide with the combination of ammonium bicarbonate and N,N-dimethylformamide as a cyanide source is achieved, providing nitriles in moderate to good yields. This new approach represents an exceedingly practical and safe method for the synthesis of aryl nitriles.     

Copper-mediated cyanation of aryl boronic acids using benzyl cyanide

An efficient copper-mediated synthesis of aryl nitriles from aryl boronic acids has been achieved using benzyl cyanide as a user-friendly cyanide source. Various aryl boronic acids underwent the reaction smoothly, affording the corresponding aryl nitriles in moderate to good yields. tert-Butyl hydroperoxide (TBHP) was found to be a critical agent facilitating the cyanation reaction.     

Dual Lewis acid-Lewis base activation in enantioselective cyanation of aldehydes using acetyl cyanide and cyanoformate as cyanide sources

Dual activation by a chiral Lewis acid and an achiral or chiral Lewis base enabled cyanation of both aromatic and aliphatic aldehydes with acetyl cyanide and ethyl cyanoformate to provide direct access to O-acetylated and O-alkoxycarbonylated cyanohydrins, respectively, under mild conditions. With a combination of a Ti-salen catalyst and Et3N, benzaldehyde was converted to the O-acetylated cyanohydrin with 94% ee within 10 h at -40 degrees C in 89% isolated yield.     

Copper-catalyzed cyanation of aryl iodide with the combined cyanide source of urea and DMSO

A simple copper-catalyzed cyanation of aryl iodide with the combination of urea and dimethyl sulfoxide as a cyanide source is achieved, providing nitriles in moderate to good yields. This new approach represents an exceedingly practical and safe method for the synthesis of aryl nitriles.     

Copper-catalyzed regioselective alkylation of heteroarenes with functionalized alkyl halides

The Cu-catalyzed regioselective alkylation of heteroarenes with functionalized primary, secondary, and tertiary alkyl halides is reported. The reaction proceeds via the copper-catalyzed addition of alkyl radicals to a wide range of heteroarenes, including coumarin, quinolinone, naphthoquinone, and benzofuran derivatives, with a broad substrate scope and wide functional group tolerance.     

Palladium-catalyzed cyanation of propargylic carbonates with trimethylsilyl cyanide

[reaction: see text]An equimolar mixture of propargylic carbonate (1) and trimethylsilyl cyanide (2) in THF under reflux affords cyanoallene (3) in the presence of a catalytic amount (5 mol %) of Pd(PPh3)4. In the reaction, the trimethylsilyl moiety of 2 effectively traps the leaving group of 1. The use of 2 in excess (6 equiv) provides dicyanated products (7 or 8) in high yields.     

Copper-catalyzed direct cyanation of terminal alkynes with benzoyl cyanide

Copper-catalyzed direct cyanation of terminal alkynes is achieved using less toxic, stable and easy to handle benzoyl cyanide as a cyanide source and air as an oxidant. This protocol provides a good alternative to the preparation of 3-arylpropiolonitriles under mild condition.     

Ligand-free CuI-catalyzed cyanation of aryl halides using K4[Fe(CN)6] as cyanide source and water as solvent

A methodology for the cyanation of aryl iodides is reported using copper iodide as the catalyst, K₄[Fe(CN)₆] as the cyanide source, and small quantities of water and tetraethylene glycol as the solvent. Reactions are complete within 30 min of microwave heating at 175 °C. A simple work-up procedure has also been devised.     

The palladium-catalyzed cyanation of indole C-H bonds with the combination of NH4HCO3 and DMSO as a safe cyanide source

A palladium-catalyzed cyanation of the 3-position of indole sp(2) C-H bonds by the combination of NH(4)HCO(3) and DMSO as the "CN" source was achieved to provide aromatic nitriles in moderate to good yields with excellent regioselectivity. It represents a practical and safe cyanation method.     

Aerobic ruthenium-catalyzed oxidative cyanation of tertiary amines with sodium cyanide

RuCl3-catalyzed oxidative cyanation of tertiary amines with sodium cyanide under molecular oxygen (1 atm) at 60 degrees C gives the corresponding alpha-aminonitriles, which are versatile synthetic intermediates of various compounds such as amino acids and unsymmetrical 1,2-diamines, in excellent yields. This reaction is clean and should be an environmentally benign and useful process.     

Palladium‐catalyzed cyanation reaction of aryl halides using K4[Fe(CN)6] as non‐toxic source of cyanide under microwave irradiation

An efficient method for preparation of aryl nitriles—using [Pd{C₆H₂(CH₂CH₂ NH₂)‐(OMe)₂,3,4} (µ‐Br)]₂ complex as an efficient catalyst and K₄[Fe(CN)₆] as a green cyanide source—from aryl bromides, aryl iodides and aryl chlorides under microwave irradiation has been reported. This complex has been demonstrated to be an active and efficient catalyst for this reaction. Using a catalytic amount of this synthesized palladium complex in DMF at 130 °C led to production of the cyanoarenes in excellent yields in short reaction times. Copyright © 2010 John Wiley & Sons, Ltd.     

Palladium-catalyzed cyanation of aryl halides using K4[Fe(CN)6] as cyanide source, water as solvent, and microwave heating

A methodology for the cyanation of aryl iodides and activated aryl bromides is reported using water as the solvent and K₄[Fe(CN)₆] as the cyanide source. Reactions are complete within 20 min.     

A palladium-catalyzed one-pot procedure for the regioselective dimerization and cyanation of indoles

A one-pot method for the regioselective dimerization and cyanation of indoles has been developed. The reaction uses safe and nontoxic K₄[Fe(CN)₆]·3H₂O as the cyanating agent which introduces selectively a cyano group into the 3-position of biindoles with high efficiency.     

A method for the cyanation of alkenes using nitromethane as a source of cyano group mediated by proton-exchanged montmorillonite

A novel method for the cyanation of alkenes using nitromethane as a source of the cyano group is described. H⁺-montmorillonite mediates the cyanation through the in situ formation of trimethylsilanecarbonitrile oxide from nitromethane and allylsilane, followed by 1,3-dipolar cycloaddition and subsequent rearrangement to afford the corresponding nitriles.     

Regioselective 1,4-conjugate hydrocyanation of dienones using potassium hexacyanoferrate(II) as an eco-friendly cyanide source

A highly regioselective 1,4-conjugate hydrocyanation of dienones using potassium hexacyanoferrate(II) as an original eco-friendly cyanide source, benzoyl chloride as a promoter and potassium carbonate as a catalyst is described. This protocol has advantages of non-toxic cyanating agent, high regioselectivity, high yield, and simple work-up procedure.