4073-48-7

Upstream product

• 4360-47-8 cinnamonitrile 
• 28446-70-0 (E/Z)-3-(4-methylphenyl)propenenitrile 
• 71-43-2 benzene 
• 176445-14-0 (E)-3-(4-methylphenyl)-3-phenyl-2-propenenitrile 
• 624-31-7 4-tolyl iodide 
• 28446-70-0 (E)-4-methylcinnamonitrile 
• 104-87-0 4-methyl-benzaldehyde 
• 108-88-3 toluene 

Downstream Products

• 4073-52-3 3-(4-methylphenyl)-3-phenylpropan-1-amine 

Relevant academic research and scientific papers

Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions: Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones

Reactions of 3-arylpropenenitriles [ArCH[dbnd]CHCN] with arenes [Ar'H] under the superelectrophilic activation conditions with Br?nsted superacid TfOH (CF3SO3H) or strong Lewis acid AlBr3 result, first, in the formation of products of hydroarylation of the carbon-carbon double bond, 3,3-diarylpropanenitriles [Ar(Ar’)CHCH2CN]. Reactions may go further in TfOH leading to 3-arylindanones, as products of intramolecular aromatic acylation by the electrophilically activated nitrile group. Intermediate cationic species, derived at the protonation of the starting 3-arylpropenenitriles onto the carbon of C[dbnd]C bond and the nitrile nitrogen, have been studied by DFT calculation. A plausible reaction mechanism including the formation of highly reactive dications [(Ar)HC+–CH2C+ = NH] has been proposed. The obtained 3,3-diarylpropanenitriles have been transformed into pharmaceutically valuable 5-(2,2-diarylethyl)-1H-tetrazoles [Ar(Ar’)CHCH2Tetr] and 3-diarylpropylamines [Ar(Ar’)CH(CH2)2NH2] by the reactions with NaN3 and LiAlH4 correspondingly.

Cinnamonitrile as a precursor of a bi-centered electrophile in reactions with arenes in triflic acid

The reaction of cinnamonitrile [PhCH = CHCN] with arenes in the superacid TfOH at room temperature for 1 h gave two types of compounds, 3-aryl-3-phenyl propionitriles [Ar(Ph)CHCH2CN] and/or 3-phenylindanones in 28–76% yield. The formation of these two reaction products depends on the nucleophilicity of the arene. In these reactions, carbocations generated upon the protonation of cinnamonitrile in TfOH behave as bi-centered electrophiles possessing reactive centers on the C3 carbon of the double bond and on the C1 carbon of the nitrile group.

Highly efficient Rh-catalyzed asymmetric hydrogenation of α,β-unsaturated nitriles

A highly efficient enantioselective hydrogenation of α,β-unsaturated nitriles catalyzed by Rh-(R,R)-f-spiroPhos complex has been developed. With Rh-(R,R)-f-spiroPhos catalyst and under mild conditions, a wide range of α,β-unsaturated nitriles including the (E)- and (Z)-isomers of 3-alkyl-3-aryl, 3,3-diaryl, and 3,3-dialkyl α,β-unsaturated nitriles were hydrogenated to the corresponding chiral nitriles with excellent enantioselectivities (up to 99.9% ee) and high turnover numbers (TON up to 10,000).

Copper-catalyzed 1,4-addition of organoboronates to alkylidene cyanoacetates: Mechanistic insight and application to asymmetric catalysis

In addition: A copper/N-heterocyclic carbene(NHC)-catalyzed 1,4-addition of organoboronates to alkylidene cyanoacetates was developed, in which the catalytic cycle is proposed to consist of a transmetalation/insertion/ligand exchange. An effective asymmetric variant has also been achieved by the use of a chiral NHC ligand (see scheme). Copyright

Asymmetrie synthesis of 1,1-diarylalkyl units by a copper hydride catalyzed reduction: Differentiation between two Similar aryl substituents

An efficient method for the preparation of enantiomerically enriched 1,1-diarylalkyl units has been developed. The use of copper hydride complexed by the (R)-1-[(5)-2-diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine (Josiphos) ligand effects a highly enantioselective conju-gate reduction of β,β-diaryl-substituted α,β-unsaturated nitriles with aryl groups of similar steric demand and no secondary coordination site. A range of substrates with meta and para substituents on the aryl group were reduced with good to excellent enantioselectivities (up to 97% enantiomeric excess (ee)) and this methodology was applied to the formal synthesis of indatraline.

Rhodium/chiral diene-catalyzed asymmetric 1,4-addition of arylboronic acids to arylmethylene cyanoacetates

Asymmetric 1,4-addition of arylboronic acids to (￡)-methyl 2-cyano-3-arylpropenoates proceeded in the presence of a rhodium catalyst (3 mol %) coordinated with a chiral diene ligand, (R,R)-Ph-bod*, to give high yields of the corresponding methyl 3,3-diaryl-2-cyanopropanoates with high enantioselectivity (up to 99% ee). This catalytic asymmetric transformation was applied to the asymmetric synthesis of (R)-tolterodine. American Chemical Society.

Copper-catalyzed asymmetric reduction of 3,3-diarylacrylonitriles

Equation Presented CuH-catalyzed enantioselective conjugate reduction of 3,3-diaryl-substituted acrylonitriles is described. A range of 3-aryl-3-pyridylacryionitriles were reduced with high levels of enantioselectivity under optimal conditions employing a

COMPARATIVE REACTIVITY OF NITRILES OF PARA-SUBSTITUTED CINNAMIC ACIDS IN THE ALKYLATION OF BENZENE IN THE PRESENCE OF ALUMINUM CHLORIDE

The relative rate constants for the reactions of the nitriles of p-methoxy, p-methyl, and p-chlorocinnamic acids with benzene in the presence of aluminum chloride were determined by the method of competing reactions in relation to cinnamonitrile.The negative sign of ρ indicates that the electrophilic stage of complex formation between the unsaturated nitrile and aluminum chloride has a deciding role in the alkylation process.