The facile dearomatization of nitroaromatic compounds using lithium enolates of unsaturated ketones in conjugate additions and (4+2) formal cycloadditions

The dearomatization of conventional nitroarenes by lithiated enolates derived from methyl vinyl ketones easily takes place, following a formal (4+2) cycloaddition process. While nitroindoles react readily with in situ generated conjugated enolates, the deaggregation of these latter species using HMPA extends the reaction scope to the more aromatic nitronaphthalenes and pyridines. The novel nucleophilic activation of enolizable unsaturated ketones allows their addition to nitroaromatics and furnishes the corresponding formal dearomatized (4+2) cycloadducts.