Versatile functionalization of electron rich-fused heterocyclic arenes via electrophilic aromatic addition reaction and their applications

Abstract

Divergent functionalized 8-methoxyquinaldines were synthesized via regioselective debromination, 1,3-bromine shift process, aromatization with treatment of a strong base, nucleophilic substitution reaction at the C7 position using amines and cyanide as a nucleophile in the absence of a metal source and a catalyst from an unusual electrophilic aromatic addition (AdEAr) reaction products 7 and 8. In addition, quinaldine-7,8-dione was prepared by presence of CAN (ceric ammonium nitrate) in AcOH and H2O for 10 min at room temperature from N-(alkylamino)-8-methoxyquinalidines. During the AdEAr reaction, new stereoselective dearomatized addition products were generated via discriminative reaction routes depending on the methoxy and bromine occupancy position. The AdEAr reaction not only allowed for the functionalization of electron rich-fused heterocyclic arenes, but also provided a new synthetic route to an alternative mechanism for electrophilic aromatic substitution reactions.