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 language | English |
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Pages (from-to) | 1207-1215 |
Number of pages | 9 |
Journal | Organometallics |
Volume | 18 |
Issue number | 7 |
DOIs | |
Publication status | Published - Mar 29 1999 |
Externally published | Yes |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry