Selective Activation of Unstrained C(O)–C Bond in Ketone Suzuki–Miyaura Coupling Reaction Enabled by Hydride-Transfer Strategy

A Rh­(I)-catalyzed ketone Suzuki–Miyaura coupling reaction of benzylacetone with arylboronic acid is developed. Selective C­(O)–C bond activation, which employs aminopyridine as a temporary directing group and ethyl vinyl ketone as a hydride acceptor, occurs on the alkyl chain containing a β-position hydrogen. A series of acetophenone products were obtained in yields up to 75%.