6443-81-8

Upstream product

• 140-29-4 phenylacetonitrile 
• 637-59-2 1-Bromo-3-phenylpropane 
• 67-56-1 methanol 
• 6443-79-4 1t.4-diphenyl-pentadien-(1.3ξ)-oic acid-(5)-nitrile 
• 122-97-4 3-Phenyl-1-propanol 
• 100-42-5 styrene 
• 119072-55-8 tert-butylisonitrile 
• 17376-04-4 2-phenethyl iodide 
• 16532-79-9 4-Bromophenylacetonitrile 

Downstream Products

• 5407-91-0 1,4-diphenylbutan-1-one 
• 22055-24-9 2,5-diphenylvaleric acid 
• 1431331-59-7 C₂₇H₂₆Cl₂N₄ 
• 22228-41-7 5-oxo-2,5-diphenylpentanenitrile 
• 118386-77-9 6-Phenyl-6,7,8,9-tetrahydro-benzocyclohepten-5-one oxime 
• 73206-05-0 3-phenyl-1,2,3,4,5,6-hexahydro-1-benzazocin-2-one 
• 51197-89-8 2-phenyl-1-benzosuberone 

Relevant academic research and scientific papers

Three-Component Visible-Light-Induced Palladium-Catalyzed 1,2-Alkyl Carbamoylation/Cyanation of Alkenes

A mild visible-light-induced Pd-catalyzed one-pot three-component alkyl-carbamoylation and cyanation of alkenes was developed. This general transformation, which proceeds via the in situ formation of a reactive ketenimine intermediate, allows for a rapid construction of a broad range of valuable amides and nitriles from readily available alkenes, alkyl iodides, and isocyanides. An efficient synthesis of tetrazole and amidine via this approach was also demonstrated.

Catalyst for α alkylation of nitriles and uses thereof

The invention discloses a nitrile alpha-alkylation reaction catalyst and application thereof. The nitrile alkylation reaction catalyzed by pyridine-pyridine-imidazoline asymmetric pincerlike rutheniumcompounds has a reaction general formula shown in the specification, and in the general formula, a catalyst is a pyridine-pyridine-imidazoline asymmetric pincerlike ruthenium compound, R1 is aryl, and R2 is aryl or alkyl, wherein aryl is phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl, thiophene and the like, and alkyl is n-butyl, phenylpropyl and the like. The synthesis method comprisesthe following synthesis steps: adding an asymmetric pincerlike ruthenium compound, an alkali, a nitrile compound and an alcohol into a solvent for reaction, and after the reaction is finished, conducting separating and purifying to obtain a corresponding target product. Alcohol is used as an alkylating reagent, generated water is a unique by-product, the method conforms to the ideas of atom economy and environmental friendliness, and meanwhile, the method has the advantages of use of a catalytic amount of alkali, short reaction time, economy and the like.

α-Alkylation of Nitriles with Alcohols Catalyzed by NNN′ Pincer Ru(II) Complexes Bearing Bipyridyl Imidazoline Ligands

A series of unsymmetrical NNN′ ruthenium(II) complexes supported by a tridentate bipyridyl imidazoline ligand with variable steric hindrance (2a-c; R1 = tBu, iPr, or Bn) and electronic effect (2d-h; R2 = H, CH3, OCH3, Br, or NO2) were prepared. The molecular structures of ligands 1f and 1g, and Ru complex 2a were further determined by X-ray single-crystal diffraction. The catalytic activity of these eight complexes for α-alkylation of nitriles with alcohols was evaluated, which could be controlled by the substituents on the imidazoline moiety. Ru complex 2h bearing a strong electron-withdrawing group (R2 = NO2) demonstrated the highest catalytic activity, with alkylated nitriles achieved in up to 97% yield.

Iron-Catalyzed Alkylation of Nitriles with Alcohols

A general, efficient iron-catalyzed α-alkylation of nitriles with primary alcohols through a hydrogen-borrowing pathway has been developed, allowing a wide variety of alkylated nitriles to be readily accessible. Detailed mechanistic studies suggest that the reaction proceeds via an olefin intermediate with the turnover rate limited by the hydrogenation of the olefin with an iron hydride. Apart from participating in the alkylation, the nitrile is found to play an important role in promoting the formation of and stabilizing the active catalytic species.

Facile Ruthenium(II)-Catalyzed α-Alkylation of Arylmethyl Nitriles Using Alcohols Enabled by Metal-Ligand Cooperation

A facile ruthenium(II)-catalyzed α-alkylation of arylmethyl nitriles using alcohols is reported. The ruthenium pincer catalyst serves as an efficient catalyst for this atom-economical transformation that undergoes alkylation via borrowing hydrogen pathways, producing water as the only byproduct. Arylmethyl nitriles containing different substituents can be effectively alkylated using diverse primary alcohols. Notably, using ethanol and methanol as alkylating reagents, challenging ethylation and methylation of arylmethyl nitriles were performed. Secondary alcohols do not undergo alkylation reactions. Thus, phenylacetonitrile was chemoselectively alkylated using primary alcohols in the presence of secondary alcohols. Diols provided a mixture of products. When deuterium-labeled alcohol was used, the expected deuterium transposition occurred, providing both α-alkylation and α-deuteration of arylmethyl nitriles. Consumption of nitrile was monitored by GC, which indicated the involvement of first-order kinetics. Plausible mechanistic pathways are suggested on the basis of experimental evidence. The ruthenium catalyst reacts with base and generates an unsaturated intermediate, which further reacts with both nitriles and alcohols. While nitrile is transformed to enamine via [2 + 2] cycloaddition, alcohol is oxidized to aldehyde. The metal bound enamine adduct reacts with aldehyde via Michael addition, resulting in an ene-imine adduct, which perhaps undergoes direct hydrogenation by a Ru dihydride intermediate, produced from alcohol oxidation. However, in situ monitoring of the reaction mixture confirmed the presence of unsaturated vinyl nitrile in the reaction mixture in minor amounts (10%), indicating the possible dissociation of ene-imine adduct during the catalysis, which may further be hydrogenated to provide the α-alkylated nitriles. Overall, the efficient α-alkylation of nitriles using alcohols can be attributed to the amine-amide metal-ligand cooperation that is operative in the ruthenium pincer catalyst, which enables all of the catalytic intermediates to remain in the +2 oxidation state throughout the catalytic cycle.

Pyridinylpyrimidines selectively inhibit human methionine aminopeptidase-1

Cellular protein synthesis is initiated with methionine in eukaryotes with few exceptions. Methionine aminopeptidases (MetAPs) which catalyze the process of N-terminal methionine excision are essential for all organisms. In mammals, type 2 MetAP (MetAP2)

Oxidative Decyanation of Secondary Nitriles to Ketones

Procedures for the oxidative decyanation of secondary nitriles to ketones involve (1) iodination of N-(trialkylsilyl)ketenimines derived from secondary nitriles and subsequent hydrolysis of the α-iodo nitriles with silver oxide, (2) addition of nitrosobenzene to N-(trialkylsilyl)ketenimines, (3) conversion of secondary nitriles to α-(phenylthio) nitriles and subsequent hydrolysis with N-bromosuccinimide in aqueous acetonitrile, and (4) preparation of α-hydroperoxy nitriles by direct oxygenation of anions of secondary nitriles and subsequent reductive hydrolysis with stannous chloride followed by sodium hydroxide.The latter general procedure was applied to various secondary nitriles bearing dialkyl, aryl and alkyl, and diaryl substituents to provide ketones in good yield and was extended to the oxidative decyanation of α,β-unsaturated nitriles to furnish α,β-unsaturated ketones.