142611-49-2Relevant academic research and scientific papers
Isomerization of (πr-allyl)palladium complexes via nucleophilic displacement by palladium(0). A common mechanism in palladium(0)-catalyzed allylic substitution
Granberg, Kenneth L.,B?ckvall, Jan-E.
, p. 6858 - 6863 (2007/10/02)
Treatment of (π-allyl)palladium complexes such as 6 and 9 with Pd(PPh3)4 leads to rapid isomerization at -15 °C in tetrahydrofuran and other solvents. At 0°C and in the presence of more than 2 equiv of triphenylphosphine per palladium, the phosphine attacks the T-allyl group to give allylic phosphonium salts 7 with concomitant formation of a palladium(0)-phosphine complex, and isomerization of 6 is observed. Attack by PPh3 on 6 was shown to be stereospecific and to proceed with inversion. Studies of the Pd(0)-catalyzed substitution of le (X = OAc) with several different nucleophiles support the hypothesis that Pd(0) acts as a nucleophile on (π-allyl)palladium complexes, in a reaction that leads to loss of stereospecificity in these systems.
