Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation

A zirconocene dichloride‐catalyzed alkene hydrosilylation is reported that can be applied to non‐activated and conjugated terminal and internal alkenes. It involves a catalytic Zr‐walk process and leads to a selective conversion to the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases the applicability and operational simplicity in comparison to earlier zirconium(II)‐based protocols. Supported by additional experiments and calculations, a mechanism via zirconium(IV) intermediates is proposed. Due to the benign nature and ready‐availability of the zirconium catalyst, the reaction is an attractive alternative to established alkene hydrosilylation methods. A new protocol for the zirconium‐catalyzed hydrosilylation of alkenes is presented that allows the direct use of zirconocene dichloride as catalyst through mild activation with a methoxide additive. The reaction can be applied to terminal, internal, and conjugated alkenes. A catalytic zirconium walk ensures the selective formation of linear silane products. Based on additional experiments and calculations, a zirconium(IV) mechanism is proposed.