LAUSR

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 Ru3(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 C(aryl)–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.