32970-77-7

Upstream product

• 10077-34-6 2-phenyl-3-p-tolyl-acrylonitrile 
• 100-51-6 benzyl alcohol 
• 25125-29-5 (Z)-α-phenyl-β-(p-tolyl)acrylonitrile 
• 589-18-4 4-Methylbenzyl alcohol 
• 140-29-4 phenylacetonitrile 
• 16532-79-9 4-Bromophenylacetonitrile 

Downstream Products

• 78141-21-6 4-(4-methylphenyl)-3-phenyl-2-butanone 
• 80654-60-0 (±)-3-(4-methylphenyl)-2-phenylpropanoic acid 

Relevant academic research and scientific papers

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 arylacetonitriles with primary alcohols catalyzed by backbone modified N-heterocyclic carbene iridium(i) complexes

A series of backbone-modified N-heterocyclic carbene (NHC) complexes of iridium(i) (1d-f) have been synthesized and characterized. The electronic properties of the NHC ligands have been assessed by comparison of the IR carbonyl stretching frequencies of thein situprepared [IrCl(CO)2(NHC)] complexes in CH2Cl2. These new complexes (1d-f), together with previously prepared1a-c, were applied as catalysts for the α-alkylation of arylacetonitriles with an equimolar amount of primary alcohols or 2-aminobenzyl alcohol. The catalytic activities of these complexes could be controlled by modifying the N-substituents and backbone of the NHC ligands. The NHC-IrIcomplex1fbearing 4-methoxybenzyl substituents on the N-atoms and 4-methoxyphenyl groups at the 4,5-positions of imidazole exhibited the highest catalytic activity in the α-alkylation of arylacetonitriles with primary alcohols. Various α-alkylated nitriles and aminoquinolines were obtained in high yields through a borrowing hydrogen pathway by using 0.1 mol%1fand a catalytic amount of KOH (5 mol%) under an air atmosphere within significantly short reaction times.

Nickel-catalyzed hydrogen-borrowing strategy: Chemo-selective alkylation of nitriles with alcohols

The first nickel-catalyzed hydrogen-borrowing alkylation of a series of aryl acetonitriles with a variety of aryl, heteroaryl, allylic and alkyl alcohols releasing water as the by-product (>33 examples, up to 90% yield) is reported.

Ru(II)-PBTNNXN complex bearing functional 2-(pyridin-2-yl)benzo[d]thiazole ligand catalyzed α-alkylation of nitriles with alcohols

Six tridentate NNN ligand precursors derived from 2-(pyridin-2-yl)benzo[d]thiazole(PBT) with different linkers, PBTNNXN (X = NH, NMe, O, S) (1a–1f), have been successfully prepared. The electronic properties of PBTNNXN ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron-donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) have been characterized by NMR spectroscopy, high-resolution mass spectroscopy, and Fourier transform infrared (FT-IR). The molecular structures of 1f, 2a, and 2f have been determined by X-ray diffraction study. The results indicate that PBTNNNHN ligand in the complex presented coplanar with two five-membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α-alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru-H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle.

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.

Sustainable Alkylation of Nitriles with Alcohols by Manganese Catalysis

A general and chemoselective catalytic alkylation of nitriles using a homogeneous nonprecious manganese catalyst is presented. This alkylation reaction uses naturally abundant alcohols and readily available nitriles as coupling partners. The reaction tolerates a wide range of functional groups and heterocyclic moieties, efficiently providing useful cyanoalkylated products with water as the only side product. Importantly, methanol can be used as a C1 source and the chemoselective C-methylation of nitriles is achieved. The mechanistic investigations support the multiple role of the metal-ligand manganese catalyst, the dehydrogenative activation of the alcohol, α-C-H activation of the nitrile, and hydrogenation of the in-situ-formed unsaturated intermediate.

Base-Promoted α-Alkylation of Arylacetonitriles with Alcohols

A practical method to synthesize α-alkylated arylacetonitriles from arylacetonitriles and alcohols without using any expensive transition metal complexes is demonstrated here. Following this base-catalysed sustainable procedure, various arylacetonitriles were successfully alkylated with different alcohols. The practical applicability of this protocol was extended by one-pot synthesis of important carboxylic acid derivatives.

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.

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen.