Ruthenium(0)-Catalyzed Cross-Coupling of Anilines with Organoboranes by Selective Carbon-Nitrogen Cleavage

Selective activation of neutral carbon-nitrogen bonds is of great synthetic importance, because amines are among the most prevalent motifs across organic and bioactive molecules. Herein, we report the Ru(0)-catalyzed selective cleavage of neutral C(aryl)-N bonds in generic aniline derivatives enabled by a combination of Ru-3(CO)(12) and an imino auxiliary. These mild conditions provide a direct route to high-value biaryl ketones and biaryl aldehydes after facile in situ hydrolysis. A broad range of organoboranes and anilines can be coupled with high C-N cleavage selectivity. Most crucially, the reaction achieves exquisite selectivity for activation of C(aryl)-N bonds in the presence of typically more kinetically favorable Caryl)-H bonds. The method provides a strategy for the construction of functionalized terphenyls by exploiting orthogonal properties of the Ru(0) catalyst system and traceless nucleophilic properties of anilines.