Studies on the structure and equilibration of (pi-allyl)palladium complexes of phosphino(oxazolinyl)ferrocene ligands
SCIE
SCOPUS
- Title
- Studies on the structure and equilibration of (pi-allyl)palladium complexes of phosphino(oxazolinyl)ferrocene ligands
- Authors
- Cho, CW; Son, JH; Ahn, KH
- Date Issued
- 2006-09-11
- Publisher
- PERGAMON-ELSEVIER SCIENCE LTD
- Abstract
- The equilibration and catalytic efficiency of (pi-allyl)Pd complexes of N,P-chelates (L), [Pd(L)( eta(3)-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(S-p)-(diphenylphosphino)ferrocene 1; 1-[4(S)-tert-butyl-2-oxazolin-2-yl]-2(R-p)-(diphenylphosphino)ferrocene 2. X: Cl- and PF6-]. Among the possible isomeric (pi-allyl)Pd complexes, only endo-syn-syn 1n 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 enantio selectivity 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 (n-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. (c) 2006 Elsevier Ltd. All rights reserved.
- Keywords
- CATALYZED ALLYLIC ALKYLATION; PI-ALLYLPALLADIUM COMPLEXES; PLANAR CHIRALITY; DIPHENYLPHOSPHINO(OXAZOLINYL)FERROCENE LIGANDS; NUCLEOPHILIC-ADDITION; ASYMMETRIC INDUCTION; PALLADIUM COMPLEXES; SUBSTITUTION; ENANTIOSELECTIVITY; MECHANISM
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/23770
- DOI
- 10.1016/j.tetasy.2006.08.002
- ISSN
- 0957-4166
- Article Type
- Article
- Citation
- TETRAHEDRON-ASYMMETRY, vol. 17, no. 15, page. 2240 - 2246, 2006-09-11
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