Aromatic‐Amide‐Derived Olefins as a Springboard: Isomerization‐Initiated Palladium‐Catalyzed Hydrogenation of Olefins and Reductive Decarbonylation of Acyl Chlorides with Hydrosilane

A highly efficient catalytic protocol for the isomerization of substituted amide-derived olefins is presented that successfully uses a hydride palladium catalyst system generated from [PdCl(2)(PPh(3))(2)] and HSi(OEt)(3). The Z to E isomerization was carried out smoothly and resulted in geometrically pure substituted olefins. Apart from the cis-trans isomerization of double bonds, the selective reduction of terminal olefins and activated alkenes was performed with excellent functional group tolerance in the presence of an amide-derived olefin ligand, and the products were obtained in high isolated yields (up to >99 %). Furthermore, the palladium/hydrosilane system was able to promote the reductive decarbonylation of benzoyl chloride when a (Z)-olefin with an aromatic amide moiety was used as a ligand.