109036-34-2Relevant 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
Gorbunova, Yelizaveta,Zakusilo, Dmitriy N.,Boyarskaya, Irina A.,Vasilyev, Aleksander V.
, (2020)
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
Gorbunova, Yelizaveta,Zakusilo, Dmitriy N.,Vasilyev, Aleksander V.
supporting information, p. 961 - 964 (2019/03/06)
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.
