Single‐Face/All‐ cis Arene Hydrogenation by a Supported Single‐Site d 0 Organozirconium Catalyst

The single‐site supported organozirconium catalyst Cp*ZrBz 2 /ZrS (Cp*=Me 5 C 5 , Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single‐face/all‐cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all‐cis‐cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H 2 delivery to a single catalyst‐bound arene face, versus any competing intramolecular arene π‐face interchange.