Triaryl-Substituted Divinyl Ketones Cyclization: Nazarov Reaction versus Friedel-Crafts Electrophilic Substitution

The acid-catalyzed cyclization of a wide range of triaryl-substituted divinyl ketones has been studied. It was found that the reaction pathway strongly depends on the nature of the aryl substituent at the a-position to the carbonyl group. An electron-rich aromatic substituent promotes the reaction to proceed through the intramolecular Friedel-Crafts electrophilic substitution giving dihydronaphthalene derivatives. In contrast, the presence of an electron-deficient substituent is favorable for the Nazarov 4 pi-conrotatory cyclization yielding triaryl-substituted cydopentenones. The electrophilic substitution reaction was applied to thiophene and thiazole derivatives.