Ruthenium-Catalyzed Carbon−Carbon Bond Formation via the Cleavage of an Unreactive Aryl Carbon−Nitrogen Bond in Aniline Derivatives with Organoboronates

The RuH 2 (CO)(PPh 3 ) 3 -catalyzed reaction of 2-amino-6-methylacetophenone with phenylboronic acid 2,2-dimethyl-1,3-propanediol ester in refluxing toluene gave the corresponding phenylation product in 83% yield via aryl carbon−nitrogen bond cleavage. This reaction involves two notable features: (1) the coupling proceeds via the oxidative addition of an aryl carbon−nitrogen bond in anilines to the ruthenium complex, and (2) C−C bond formation takes place via transmetalation between the Ru−NR 2 species and organoboronates.