Cleavage of C-N Bonds in Aniline Derivatives on a Ruthenium Center and Its Relevance to Catalytic C-C Bond Formation

The first observation of cleavage of unactivated aromatic C-N bonds on a late-transition-metal center was achieved using o-acylanilines and a ruthenium complex. Use of olefins as additives dramatically improved the rate of C-N bond cleavage. The carbon fragment remaining on the ruthenium after C-N bond cleavage was coupled with a pherylboronate to form a biphenyl framework. The present results suggest that ruthenium-catalyzed C-C bond formation from o-acylaniline and organoboronate proceeds via direct C-N bond cleavage on the ruthenium center.