Ruthenium-Catalyzed Hydrodefluorination with Silane as the Directing and Reducing Group.

We describe herein an efficient and selective Ru-catalyzed intramolecular HDF directed by a silyl group, which is readily installed, and removable and transformable following the HDF reaction. The hydrosilyl group in polyfluoroaryl silane acts not only as the directing group but also as the internal reductant, enabling precise control of the ortho-selectivity and avoiding overdefluorination. Mechanistic studies reveal a plausible catalytic cycle involving a Ru(IV)-aryne intermediate.