Functionalized magnesiated aniline derivatives were readily prepared by using a bromine- or iodine-magnesium exchange. Formamidine or benzimine were found to be excellent protecting groups of the amino function for the generation of functionalized aminated Grignard reagents. These organomagnesium reagents react with various electrophiles such as aldehydes, iodoenones and allylic halides in excellent yields. After transmetallation with ZnBr 2 , Pd(0)-catalyzed cross-coupling with aryl iodides can be readily performed.
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