A highly selective acid-promoted aryl [1,2]-rearrangement of 4-methyl-4-aryl-2,5-cyclohexadienones with 37% HCl in Ac2O was developed, and the corresponding polysubstituted meta-arylphenyl acetates were smoothly generated in 75–94% yields.
The rearrangement and demethylaromatization of cyclohexadienimines (namely cyclohexadienone imines) were developed. m-Arylanilines and p-arylanilines were respectively generated under different conditions.
Prochiral 2,5-cyclohexadienones, being stable and easily accessible, are privileged key building blocks for the synthesis of complex molecules and bioactive natural products.
A perfectly chemo- and stereoselective desymmetrization of 2,5-cyclohexadienones has been described, where the domino process is initiated by the organocatalyzed enantioselective conjugate addition to the appended 4-nitro-5-styrylisoxazoles.
A squaramide-catalyzed regio-/enantioselective sulfa-1,6-addition initiated highly enantio- and diastereoselective desymmetrization of 2,5-cyclohexadienone-tethered 3-cyano-4-styrylcoumarins has been disclosed.