TY - JOUR

T1 - Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions

T2 - Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones

AU - Gorbunova, Yelizaveta

AU - Zakusilo, Dmitriy N.

AU - Boyarskaya, Irina A.

AU - Vasilyev, Aleksander V.

N1 - Funding Information: This work was supported by the Russian Foundation for Basic Research ( RFBR , grant no. 18-33-00171 ). Spectral studies were performed at the Center for Magnetic Resonance, the Center for Chemical Analysis and Materials Research of Saint Petersburg State University, Saint Petersburg, Russia. Publisher Copyright: © 2020 Elsevier Ltd Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/6/26

Y1 - 2020/6/26

N2 - Reactions of 3-arylpropenenitriles [ArCH[dbnd]CHCN] with arenes [Ar'H] under the superelectrophilic activation conditions with Brønsted 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.

AB - Reactions of 3-arylpropenenitriles [ArCH[dbnd]CHCN] with arenes [Ar'H] under the superelectrophilic activation conditions with Brønsted 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.

KW - 3,3-Diarylpropylamines

KW - Indanones

KW - Nitriles

KW - Superelectrophilic activation

KW - Tetrazoles

KW - SUBSTITUTION

KW - TETRAZOLES

KW - INVOLVEMENT

KW - GATTERMANN

KW - HOUBEN-HOESCH

KW - MEDICINAL CHEMISTRY

KW - KETONES

KW - NITRILES

KW - FESOTERODINE

KW - TRIFLUOROMETHANESULFONIC ACID

UR - http://www.scopus.com/inward/record.url?scp=85084997557&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2020.131264

DO - 10.1016/j.tet.2020.131264

M3 - Article

AN - SCOPUS:85084997557

VL - 76

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 26

M1 - 131264

ER -