Cyano Source Research Articles

ChemInform Abstract: Copper‐Catalyzed Decarboxylative Cross‐Coupling of Cinnamic Acids and ACCN via Single Electron Transfer.

A novel and convenient method for the synthesis of β,γ-unsaturated nitriles using ACCN (1,1'-azobis(cyclohexane-1-carbonitrile)) as a cyano source was described. This reaction was amenable to a broad range of substrates and provided the desired β,γ-unsaturated nitriles containing an all-carbon quaternary carbon center in moderate yields with high selectivity via single electron transfer and decarboxylation.

Copper-catalyzed decarboxylative cross-coupling of cinnamic acids and ACCN via single electron transfer.

A novel and convenient method for the synthesis of β,γ-unsaturated nitriles using ACCN (1,1'-azobis(cyclohexane-1-carbonitrile)) as a cyano source was described. This reaction was amenable to a broad range of substrates and provided the desired β,γ-unsaturated nitriles containing an all-carbon quaternary carbon center in moderate yields with high selectivity via single electron transfer and decarboxylation.

ChemInform Abstract: Cu‐Catalyzed Cyanation of Indoles with Acetonitrile as a Cyano Source.

AbstractCyanation occurs regioselectively in 3‐position.

ChemInform Abstract: Regioselective Direct Oxidative C—H Cyanation of Quinoline and Its Derivatives Catalyzed by Vanadium‐Containing Heteropoly Acids.

A direct oxidative C–H cyanation of quinoline and its derivatives using trimethylsilyl cyanide as the cyano source and molecular oxygen as the terminal oxidant has been developed. In the presence of catalytic amounts of vanadium-containing heteropoly acids, e.g., H7PV4Mo8O40, cyanation of various quinoline and its derivatives preferentially took place at the 4-position, affording the corresponding substituted 4-cyanoquinolines as the major products.

ChemInform Abstract: Synthesis of Aryl Nitriles by Palladium‐Assisted Cyanation of Aryl Iodides Using tert‐Butyl Isocyanide as Cyano Source.

AbstractA broad range of aryl and hetaryliodides is transformed according to the title reaction in good to excellent yields.

ChemInform Abstract: Acetonitrile as a Cyanating Reagent: Cu‐Catalyzed Cyanation of Arenes.

A novel approach to the Cu-catalyzed cyanation of simple arenes using acetonitrile as an attractive cyano source has been documented. The C–H functionalization of arenes without directing groups involves a sequential iodination/cyanation to give the desired aromatic nitriles in good yields. A highly efficient Cu/TEMPO system for acetonitrile C–CN bond cleavage has been discovered. TEMPO is used as a cheap oxidant and enables the reaction to be catalytic in copper. Moreover, TEMPOCH2CN 6 has been identified as the active cyanating agent and shows high reactivity for forming the −CN moiety.

Cu-Catalyzed Cyanation of Indoles with Acetonitrile as a Cyano Source.

Cu-catalyzed cyanation of indoles with acetonitrile for the synthesis of 3-cyanoindoles has been developed. The Cu/TEMPO/(Me3Si)2 system has been identified to promote highly efficient and selective C-H cyanation of indoles by use of unactivated acetonitrile as a cyano source via a sequential iodination/cyanation process in one pot. This reaction furnishes 3-cyanoindoles in moderate to good yields and tolerates a series of functional groups. Moreover, low-cost copper catalysts and hazardless acetonitrile as a cyano source feature the practicability of this reaction.

ChemInform Abstract: Rhodium(III)‐Catalyzed Selective C—H Cyanation of Indolines and Indoles with an Easily Accessible Cyano Source.

AbstractA facile access to C‐7 cyanated indolines and C‐2 cyanated indoles using N‐cyano‐N‐phenyl‐para‐methylbenzenesulfonamide (II) as CN‐source is presented.

Synthesis of aryl nitriles by palladium-assisted cyanation of aryl iodides using tert-butyl isocyanide as cyano source

A palladium-catalyzed synthesis of aryl nitriles by the cyanation of aryl iodides with tert-butyl isocyanide as cyano source has been developed. This novel and efficient method avoids the use of toxic cyanides. The reaction is easy-to-handle and shows good functional group compatibility.

Acetonitrile as a cyanating reagent: Cu-catalyzed cyanation of arenes.

A novel approach to the Cu-catalyzed cyanation of simple arenes using acetonitrile as an attractive cyano source has been documented. The C-H functionalization of arenes without directing groups involves a sequential iodination/cyanation to give the desired aromatic nitriles in good yields. A highly efficient Cu/TEMPO system for acetonitrile C-CN bond cleavage has been discovered. TEMPO is used as a cheap oxidant and enables the reaction to be catalytic in copper. Moreover, TEMPOCH2CN 6 has been identified as the active cyanating agent and shows high reactivity for forming the -CN moiety.

ChemInform Abstract: Copper‐Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes: Convenient Synthesis of CF3‐Containing Alkyl Nitriles.

Abstract A copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which the less reactive Togni reagent 2 was used as a CF3 source and TMSCN was employed as a cyano source. Both activated and unactivated alkenes were suitable for this transformation to give CF3-containing organonitriles under mild conditions.

Rhodium(III)‐Catalyzed Selective CH Cyanation of Indolines and Indoles with an Easily Accessible Cyano Source

AbstractThe rhodium‐catalyzed selective cyanation of CH bonds of indolines and indoles with N‐cyano‐N‐phenyl‐para‐methylbenzenesulfonamide is described. This protocol offers a facile access to C‐7 cyanated indolines and C‐2 cyanated indoles with high site selectivity and excellent functional group tolerance.magnified image

Regioselective direct oxidative C-H cyanation of quinoline and its derivatives catalyzed by vanadium-containing heteropoly acids.

A direct oxidative C-H cyanation of quinoline and its derivatives using trimethylsilyl cyanide as the cyano source and molecular oxygen as the terminal oxidant has been developed. In the presence of catalytic amounts of vanadium-containing heteropoly acids, e.g., H7PV4Mo8O40, cyanation of various quinoline and its derivatives preferentially took place at the 4-position, affording the corresponding substituted 4-cyanoquinolines as the major products.

ChemInform Abstract: Palladium‐Catalyzed Cyanation of Quinazoline‐4‐tosylates for Access to 4‐CN‐Functionalized Quinazolines.

A highly efficient palladium-catalyzed cyanation of quinazoline-4-tosylates is disclosed. The method is successfully developed for the direct access to various 4-CN-functionalized quinazolines, which are potentially useful as biologically and pharmaceutically active compounds. The reactions were performed under mild conditions using inexpensive copper(I) cyanide as cyano source in good to excellent yields and great functional group diversities.

Copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes: Convenient synthesis of CF3-containing alkyl nitriles

A copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which the less reactive Togni reagent 2 was used as a CF3 source and TMSCN was employed as a cyano source. Both activated and unactivated alkenes were suitable for this transformation to give CF3-containing organonitriles under mild conditions.

Nucleophilic Attack of α‐Aminoalkyl Radicals on CarbonNitrogen Triple Bonds to Construct α‐Amino Nitriles: An Experimental and Computational Study

A new reactivity pattern of α-aminoalkyl radicals, involving nucleophilic attack on C≡N triple bonds under thermal conditions, has been developed to construct α-amino nitriles. In contrast to previous C-H functionalization of tertiary amines involving α-aminoalkyl radicals, this methodology does not require the use of photocatalytic conditions or a transition-metal catalyst. Inexpensive and nontoxic phenylacetonitrile was chosen as cyano source for this α-aminonitrile forming reaction. A plausible mechanism is proposed based upon experimental and computational results. An α-aminoalkyl radical intermediate and benzoyl cyanide have been shown to be key intermediates in this green and mild radical process. Nucleophilic attack of the α-aminoalkyl radical on the C≡N bond of PhCOCN followed by an elimination step forms the desired α-aminonitrile and an acyl radical.

Palladium-Catalyzed Cyanation of Quinazoline-4-tosylates for Access to 4-CN-Functionalized Quinazolines

A highly efficient palladium-catalyzed cyanation of quinazoline-4-tosylates is disclosed. The method is successfully developed for the direct access to various 4-CN-functionalized quinazolines, which are potentially useful as biologically and pharmaceutically active compounds. The reactions were performed under mild conditions using inexpensive copper(I) cyanide as cyano source in good to excellent yields and great functional group diversities.

ChemInform Abstract: Palladium‐Catalyzed C(sp2)—H Cyanation Using Tertiary Amine Derived Isocyanide as a Cyano Source.

AbstractMechanistic studies indicate a tertiary carbon cation to be an intermediate.

Palladium-Catalyzed C(sp2)–H Cyanation Using Tertiary Amine Derived Isocyanide as a Cyano Source

An unprecedented palladium-catalyzed cyanation of aromatic C-H bonds by using tertiary amine derived isocyanide as a novel cyano source was developed. Cu(TFA)(2) was used as a requisite stoichiometric oxidant. Mechanistic studies suggest that a tertiary carbon cation-based intermediate is involved following the C-N bond breakage.

ChemInform Abstract: Synthesis of Acrylonitriles Through an FeCl3‐Catalyzed Domino Propargylic Substitution/Aza‐Meyer—Schuster Rearrangement Sequence.

AbstractAn unprecedented route to acrylonitriles uses propargylic alcohols and tosylhydrazine as a combined nontoxic cyano source.