Chloropalladation of propargyl thioethers: A facile synthesis of cyclopalladated compounds

The reaction of the propargyl thioethers Ph--C=C-CH(R(1))SR (R = Me, Pr-i, Ph and R(1) = H, Me) with Li2PdCl4 in methanol at room temperature produced in very good yields (70-90%) five-membered palladocycles [Pd(C(Ph)=C(Cl)CH(R(1))SR)(mu-Cl)](2). Under the same reaction conditions the homopropargylthioether Ph-C=C-(CH2)(2)SPh yielded unexpectedly the complex {Pd[S(Ph)(CH2)(3)C=O(Ph)](Cl)(mu-Cl)}(2) resulting from the hydrolysis of the C=C bond.