Palladium(0) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary

New Pd(0) olefin complexes, 2-5, of a binaphthalene-based chiral P,N(oxazol ine) auxiliary, (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-diphenylphosphino-1,1 '-binaphthyl 1, have been prepared (olefin = fumaronitrile, maleic anhydrid e, 4-cyclopentene-1,3-dione, and. dibenzylideneacetone). These compounds re veal different dynamic behavior in solution as shown by 2-D exchange spectr oscopy. Ligand 1 affords excellent enantioselectivity (up to 99% ee) in the allylic amination of a 1,3-diphenyl allyl precursor. The solid-state struc ture of [Pd(eta(3)-PhCHCHCHMe)(1)]OTf, 15, has been determined and shows tw o different diastereomeric cations within one unit cell; that is both the s i 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 rep orted and reveals las does that for 15) that the oxazoline ring of 1 is twi sted relative to the P-Pd-N coordination plane, thus placing this ring subs tituent above and not below the coordination plane. A more exact solid-stat e structure for Pd-2(dba)(3) has been determined.