Reaction of acyclic 1-(trimethylsilyloxy)-1,3-dienes with bis(acetonitrile)palladium dichloride, in benzene, affords formyl-substituted η3-allylpalladium complexes in good to excellent yield. In contrast, using palladium diacetate as the palladium(II) source produces 4-acetyloxy-substituted 2-alkenals. Excellent stereoselection in favor of the E-alkenal is usually observed. The corresponding benzoic acid esters can be prepared, with similar stereoselection, using 1-(trimethylsilyloxy)-1,3-dienes and palladium diacetate in the presence of an excess sodium benzoate.

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Palladium-Assisted Rearrangement of HC(O)C6H2(OMe)3-3,4,5 to HC(O)6H2( OMe)3-2,3,4.X-Ray Structures of (PdR-(PPh3)(bipy))(CF3SO3) (R = C6H( CHO)-6,(OMe)3-2,3,4 and C6H(CHO)-2,(OMe)3-3,4,5; bipy = 2,2'-bipyridyl) .-The diarylmercury compound (I) reacts with the palladium compounds (II) or (IX) in acetone or dichloromethane to yield the anionic complex ( III) or the rearranged neutral complex (X) which are converted into the salts (VIII) or (XI) by consecutive reaction with 2,2'-bipyridyl ( IV) and triphenylphosphine (VI)/potassium triflate (VII). (Crystal data of (VIII): monoclinic, space group P21/n, Z = 4; of (XI): triclinic, space group P1, Z = 2). -(VICENTE, J.; ABAD, J.-A.; STIAKAKI, M.-A.; JONES, P. C.; J. Chem. Soc., Chem.