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

Transition‐Metal‐Free Synthesis of 1‐Indanone Skeleton: A Brief Update

“…Cyclization could also be possible from nitrile 15 a to the indanone 16 a in the presence of triflic acid. The authors also carried out almost similar type of reaction involving cinnamonitrile as a precursor [31] …”

DFT insights into superelectrophilic activation of α,β-unsaturated nitriles and ketones in superacids

“…9,11,[30][31][32] It is not surprising, therefore, that these and analogous species have been repeatedly proposed as key superelectrophilic 2 intermediates in the corresponding reactions with weak nucleophiles, such as benzene, deactivated aromatics and alkanes. 6,[8][9][10][11][12][13][14][15][16][17][18][19][20][22][23][24][25][26]33 On the other hand, perhaps the most widely proposed candidate for the role of a strong electrophile derived from α,β-enones in superacids is the O,O-diprotonated form 6 (Fig. 4).…”

“…undergo a specific kind of electrophilic activation upon action with strong Brønsted or Lewis acids. 1–25 This allowed involving them in a large variety of Friedel–Crafts type transformations, offering quite appealing synthetic solutions. Fig.…”

“…9,11,30–32 It is not surprising, therefore, that these and analogous species have been repeatedly proposed as key superelectrophilic 2 intermediates in the corresponding reactions with weak nucleophiles, such as benzene, deactivated aromatics and alkanes. 6,8–20,22–26,33…”

AlBr3-Promoted stereoselective anti-hydroarylation of the acetylene bond in 3-arylpropynenitriles by electron-rich arenes: synthesis of 3,3-diarylpropenenitriles

“…Recently, we have shown that reactions of 3-arylpropenenitriles (cinnamonitriles, ArCH=CHCN) with arenes (Ar′H) under the superelectrophilic activation by the Brønsted superacid CF 3 SO 3 H (TfOH, triflic acid) or the strong Lewis acid AlBr 3 result in the formation of 3,3-diarylpropanenitriles (Ar(Ar′)CHCH 2 CN) through the regioselective hydroarylation of the carbon–carbon double bond. In TfOH, the reactions proceed further to 3-arylindanones, as products of the intramolecular aromatic acylation of the 3,3-diarylpropanenitriles by the electrophilically activated nitrile group [ 16 – 17 ]. Based on this study and our work on electrophilic transformations of alkynes [ 18 – 20 ], we investigated reactions of 3-arylpropynenitriles under electrophilic activation conditions (see [ 21 ] for the chemistry of superelectrophilic species).…”