The effects on ligands in nucleophilic reaction of η3-allyl- palladium chloride dimers were studied. Reaction of steroid 1 with Na 2PdCl4 in concentrated HCl under CO gave the cis,trans-bis-μ-dichloro-η3-allylpalladium complex 2 after recrystallization. Reaction of 2 with malonate anion in the presence of PPh 3 afforded trans-3 in 65% yield. When Dppe was used, cis-3 was obtained as the major product. In nucleophilic reactions of bicyclic η3-allylpalladium chloride complex 4a or 4b with PPh3, cis-5 was the major product. However, the reaction with Dppe gave trans-5 predominantly. The stereo-chemistry in the nucleophilic reaction of η3-allylpalladium chloride dimer is dependent on the added phosphines.
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