کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1350697 | 980457 | 2006 | 7 صفحه PDF | دانلود رایگان |
The equilibration and catalytic efficiency of (π-allyl)Pd complexes of N,P-chelates (L), [Pd(L)(η3-PhCHCHCHPh)]X, depending on their counteranions X have been studied by NMR spectroscopy and X-ray crystallography [L: 1-[4(S)-tert-butyl-2-oxazolin-2-yl]-2(PS)-(diphenylphosphino)ferrocene 1; 1-[4(S)-tert-butyl-2-oxazolin-2-yl]-2(PR)-(diphenylphosphino)ferrocene 2. X: Cl− and PF6-]. Among the possible isomeric (π-allyl)Pd complexes, only endo-syn-syn1n and 2n and exo-syn-syn isomers 1x and 2x were observed and the endo-isomer was found to be the major one in both cases. The endo/exo ratio determined in CDCl3 at room temperature was dependent both on the counterions and more so on the N,P-chelates (Cl−: 1n/1x = 9.8/1; 2n/2x = 5.3/1 vs PF6-: 1n/1x = 8.7/1; 2n/2x = 4.6/1). The counteranions significantly affected the rate as well as the enantioselectivity in the palladium catalyzed allylic substitution reaction. In the case of Cl− counterion, the catalytic reaction proceeded much faster and also provided a higher enantioselectivity compared to the case of the PF6- counterion. We have also evaluated the relative thermodynamic stability of the palladium complexes depending on ligands 1 and 2 by an equilibration study and by X-ray crystal structure analysis for the corresponding (π-allyl)palladium complexes. The higher reactivity of the less stable palladium complex of 1 over the more stable palladium complex of 2 is explained by a steric strain-reactivity argument.
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Journal: Tetrahedron: Asymmetry - Volume 17, Issue 15, 11 September 2006, Pages 2240–2246