Catalytic Performance of Symmetrical and Unsymmetrical Sulfur-Containing Pincer Complexes: Synthesis and Tandem Catalytic Activity of the First PCS-Pincer Palladium Complex

• Published in: Chemistry : a European journal Vol. 14; no. 16; pp. 4800 - 4809
• Main Authors: Gagliardo, Marcella, Selander, Nicklas, Mehendale, Nilesh C., van Koten, Gerard, Klein Gebbink, Robertus J. M., Szabó, Kálmán J.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.01.2008; WILEY‐VCH Verlag; Wiley
• Subjects: aldol reaction; allylation; Chemistry; Chemistry, Multidisciplinary; electrophilic addition; palladium; Physical Sciences; pincer complexes; Science & Technology; CONVENIENT SYNTHESIS; aldol reaction; C-C ACTIVATION; CYCLOPALLADATED COMPOUNDS; METHYL ISOCYANOACETATE; PLATINUM(II) COMPLEXES; electrophilic addition; CARBON-CARBON BONDS; ASYMMETRIC ALDOL REACTION; HYPERBRANCHED POLYGLYCEROL; RAY CRYSTAL-STRUCTURES; palladium; allylation; pincer complexes; ELECTROPHILIC SUBSTITUTION
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.200800350

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 PPh2(BH3), 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[BF4] 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 Sn2Me6, 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. Novel catalytic features: This paper describes the development of a new unsymmetrical PCS‐pincer palladium complex (see scheme) for catalytic aldol reactions and coupling of allyl chlorides and vinyloxiranes with aldehyde and imine electrophiles. The synergic electronic effects of the phosphorus and sulfur side‐arms of this pincer complex generate novel catalytic features, one of the most interesting of which was tandem catalytic activity found for the coupling reactions of allyl chlorides with electrophiles in the presence of hexamethylditin.