Abstract
The synthesis and catalytic applications of a new aryl‐based unsymmetrical PCS‐pincer complex are reported. Preparation of the robust air‐ and moisture‐stable PCS‐pincer palladium complex 5[X] started from the symmetrical α,α′‐dibromo‐meta‐xylene and involved the selective substitution of one bromide by PPh~2~(BH~3~), followed by substitution of the second bromide by SPh and subsequent introduction of the palladium. The new PCS complexes (5[X]) were employed as catalysts in two important organic transformations. Firstly, complex 5[Cl] displays high catalytic activity in aldol reactions but enters the catalytic cycle as a precatalyst. Secondly, complex 5[BF~4~] displays tandem catalytic activity in the coupling of allyl chlorides with aldehydes and imines in the presence of hexamethylditin. In these tandem catalytic reactions the first process is the conversion of allyl chlorides into trimethylallyltin (and trimethyltin chloride) with Sn~2~Me~6~, which is followed by catalytic allylation of aldehyde and sulfonimine substrates. In addition, we present a new catalytic process for the one‐pot allylation of 4‐nitrobenzaldehyde with vinyloxirane. The catalytic performance of the novel PCS‐pincer palladium complex was compared to those of its symmetrical PCP‐ and SCS‐pincer complex analogues. It was concluded that the unsymmetrical PCS complex advantageously unifies the attractive catalytic features of the corresponding symmetrical pincer complexes including both (π‐) electron‐withdrawing (such as phosphorus) or (σ‐) electron‐donating (such as sulfur and nitrogen) heteroatoms. Thus, in the aldol reaction the PCS‐pincer palladium complex 5[X] provides a high turnover frequency, while in the tandem process both reactions are catalysed with sufficiently high activity.