Transition‐Metal‐Free Direct C−H Silylation of Electron‐Deficient Heteroarenes with Hydrosilanes via a Radical Mechanism

A direct C−H silylation of electron‐deficient heteroarenes was achieved via a radical reaction between pyridines or other N‐heterocycles and hydrosilanes in the presence of acetic acid, di‐tert‐butyl peroxide, and tert‐butyl mercaptan. The present approach allows the direct introduction of trialkylsilyl substituents at the ortho‐position of various electron‐deficient heteroarenes. Radically direct: A transition‐metal‐free direct C−H silylation of electron‐deficient heteroarenes with hydrosilanes is described. The reaction allowed regioselective insertion of silyl groups at the ortho‐positions of pyridines and N‐heterocycles. A mechanistic study suggests the reaction proceeds via a radical mechanism.