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  Preparation of Ferrocene-Containing Phosphinamine Ligands Possessing Central and Planar Chirality and Their Application in Palladium-Catalyzed Asymmetric Allylic Alkylation

Farrell, A., Goddard, R., & Guiry, P. J. (2002). Preparation of Ferrocene-Containing Phosphinamine Ligands Possessing Central and Planar Chirality and Their Application in Palladium-Catalyzed Asymmetric Allylic Alkylation. The Journal of Organic Chemistry, 67(12), 4209-4217. doi:10.1021/jo016391x.

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 Creators:
Farrell, Annette1, Author
Goddard, Richard2, Author           
Guiry, Patrick J.1, Author
Affiliations:
1Centre for Synthesis and Chemical Biology, Conway Institute of Biomolecular and Biomedical Research, Department of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland, ou_persistent22              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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 Abstract: The preparation of {2-(S-p)-[(trans-(2R,5R)-2,5- dialkylpyrrolidinyl)methyl]}ferrocenyldiphenyl phosphines, new ferrocenylphosphinamine ligands possessing one site of planar and two stereogenic centers, is described. trans-(2R,5R)-2,5- Dialkyl-1-(ferrocenylmethyl)pyrrolidines were diastereoselectively lithiated and quenched with chlorodiphenylphosphine. For the dimethyl ligand, chemical yields of up to 65% and des of up to 90% were obtained whereas the diethyl ligand afforded lower chemical Yields (10%) and des of 78%. Diastereomerically pure material was obtained in both cases after a single recrystallization from ethanol. (S)-Planar chirality was confirmed by X-ray crystallographic analysis of the dimethyl ligand. The palladium complexes of the new ligands were applied in the allylic alkylation of 1,3-diphenylprop-2- enyl acetate with reasonable chemical yields and moderate ees of up to 36% and 38% when dimethyl malonate and dimethyl methyl malonate were employed as nucleophiles, respectively. Importantly, it was found that the new ligands possessing the combination of planar and central chirality gave the opposite enantiomeric alkylation products compared to ligands which possess only the central chirality of the trans-2,5- dimethylpyrrolidinyl moiety. Solution NMR studies of the 1,3- diphenylallyl palladium complex of the dimethyl ligand revealed the presence of only the exo-configured allyl diastereomer.

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Language(s): eng - English
 Dates: 2001-12-192002-05-102002-06-01
 Publication Status: Issued
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jo016391x
 Degree: -

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Title: The Journal of Organic Chemistry
  Abbreviation : J. Org. Chem.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 67 (12) Sequence Number: - Start / End Page: 4209 - 4217 Identifier: ISSN: 0022-3263
CoNE: https://pure.mpg.de/cone/journals/resource/954925416967_1