Palladium(O) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary

Kumaravel Selvakumar, Massimiliano Valentini, Michael Wo¨rle, Paul S. Pregosin, Alberto Albinati

Research output: Contribution to journalArticle

115 Citations (Scopus)

Abstract

New Pd(0) olefin complexes, 2-5, of a binaphthalene-based chiral P,N(oxazoline) auxiliary, (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2′-diphenylphosphino-1,1′- binaphthyl, 1, have been prepared (olefin = fumaronitrile, maleic anhydride, 4-cyclopentene-1,3-dione, and dibenzylidene-acetone). These compounds reveal different dynamic behavior in solution as shown by 2-D exchange spectroscopy. Ligand 1 affords excellent enantioselectivity (up to 99% ee) in the allylic amination of a 1,3-diphenyl allyl precursor. The solid-state structure of [Pd(η3-PhCHCHCHMe)(1)]OTf, 15, has been determined and shows two different diastereomeric cations within one unit cell; that is both the si and re faces of the allyl crystallize together, the first example of this for a moderately large allyl ligand. The structure of PdCl2(1) is also reported and reveals (as does that for 15) that the oxazoline ring of 1 is twisted relative to the P-Pd-N coordination plane, thus placing this ring substituent above and not below the coordination plane. A more exact solid-state structure for Pd2(dba)3has been determined.

Original languageEnglish
Pages (from-to)1207-1215
Number of pages9
JournalOrganometallics
Volume18
Issue number7
Publication statusPublished - Mar 29 1999

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Amination
alkylation
Alkylation
Palladium
Alkenes
alkenes
palladium
Maleic Anhydrides
Ligands
solid state
ligands
Enantioselectivity
rings
Dione
anhydrides
acetone
Cations
Ion exchange
Spectroscopy
cations

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Selvakumar, K., Valentini, M., Wo¨rle, M., Pregosin, P. S., & Albinati, A. (1999). Palladium(O) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary. Organometallics, 18(7), 1207-1215.

Palladium(O) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary. / Selvakumar, Kumaravel; Valentini, Massimiliano; Wo¨rle, Michael; Pregosin, Paul S.; Albinati, Alberto.

In: Organometallics, Vol. 18, No. 7, 29.03.1999, p. 1207-1215.

Research output: Contribution to journalArticle

Selvakumar, K, Valentini, M, Wo¨rle, M, Pregosin, PS & Albinati, A 1999, 'Palladium(O) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary', Organometallics, vol. 18, no. 7, pp. 1207-1215.
Selvakumar, Kumaravel ; Valentini, Massimiliano ; Wo¨rle, Michael ; Pregosin, Paul S. ; Albinati, Alberto. / Palladium(O) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary. In: Organometallics. 1999 ; Vol. 18, No. 7. pp. 1207-1215.
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