Iron‐Catalyzed Directed C−H Silylation of Pivalophenone N−H Imines

An iron‐catalyzed, N−H imine‐directed arene C−H silylation reaction with hydrosilane has been achieved. Pivalophenone N−H imine undergoes ortho C−H silylation with triethylsilane in the presence of [Fe3(CO)12] as a catalyst and norbornene as a hydrogen acceptor. The product can be readily transformed into ortho‐silylated benzonitrile via conversion of the imine functionality to a cyano group under peroxide photolysis. Iron‐catalyzed, chelation‐assisted silylation of aromatic C−H bonds is reported. Pivalophenone N−H imines and triethylsilane undergo dehydrogenative C−Si bond formation in the presence of [Fe3(CO)12] and norbornene, affording ortho‐silylated products in moderate yields. The pivaloyl N−H imine moiety can be readily converted to a cyano group, thus allowing facile preparation of ortho‐silylated benzonitrile.