Palladium® complexes sulfur ligands

In 2004, Molander et al. developed another type of chiral sulfur-containing ligands for the intermolecular Heck reaction. Thus, their corresponding novel cyclopropane-based phosphorus/sulfur palladium complexes proved to be active as catalysts for the reaction between phenyltriflate and dihydrofuran, providing at high temperature a mixture of the expected product and its iso-merised analogue (Scheme 7.7). The major isomer C was obtained with a maximum enantioseleetivity of 63% ee. 

The most recent development concerns the heterocyclic (amino)(ylide)carbenes AYC. Such compounds have been known for some years [203] but so far had little impact compared to their diamino stabilized relatives. Both phosphorus ylide (86) and sulfur ylide (87) stabilized AYC ligands have been generated in situ and were stabilized at suitable metal centers (Fig. 27) [204, 205]. The palladium complex 88 with an anionic (amino) [bis(ylide)]carbene is also known [206]. 

The use of ligand exchange has been examined for the analysis of PTH (phenylthio-hydantoin) amino acids separated on silica gel plates [92]. The method is an extension of the procedure developed for organophosphate pesticides [84]. The chromatoplate is sprayed with a solution of palladium(II) chloride and calcein. Palladium complexes with calcein to form a non-fluorescent chelate. However, in the presence of many sulfur-containing compounds, such as PTH-amino acids, the palladium is displaced from the complex liberating free calcein which gives an intense fluorescence. This method is capable of determining 0.1-nmole amounts of PTH-amino acids. 

Nitrogen nucleophiles, in a similar manner to oxygen- and sulfur-based functionality, undergo transition metal-catalyzed cross-coupling with halopyridines. The use of palladium(O) catalysts is most effective in combination with chelating bis-(phosphine) ligands such as BINAP that prevent the formation of pyridine-palladium complexes that... 

Palladium-complex-promoted asymmetric Diels-Alder reaction stereoselective synthesis of a new sulfinyl-substituted phosphine ligand containing three carbon, one phosphorus and one sulfur stereogenic centres <95CC1747>. 

DMSO complexes have also been prepared and studied in contexts related to organome-tallic chemistiy. DMSO binds to low-valent late metals through the electron pair on sulfur, to harder high-valent metals through the electron pairs on oxygen, and to some complexes with a mixture of 0- and S-bound forms. " Palladium complexes of DMSO and of biden-tate sulfoxide ligands have been used as catalysts for the oxidative cyclization of enols and... 

---