A new and autocatalytic method was developed for Friedel‐Crafts acylation of arenes without additional catalyst and additive. A series of electron‐rich arenes underwent the acylation to give the targeted product in low to high yields by using aryl, alkyl and vinyl acyl chlorides as the acylating reagent, which gave an effective method for the preparation of diaryl ketones, alkyl aryl ketones and α,β‐unsaturated ketones. Preliminary mechanistic investigation suggested that the present acylation displayed an induction period and a sigmoid kinetic profile characteristic of autocatalytic systems, and the resulting H+ played a role of the catalyst.

Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3‐phenylacrylonitrile.

No abstract