Highly Efficient Asymmetric Lewis Acid Catalysis with Platinum Group Complexes of Conformationally Flexible 1,3-Butadiene-Bridged Diphosphines, NUPHOS

Academic Article

Abstract

  • (Matrix presented). Palladium and platinum complexes of conformationally flexible 1,3-butadiene-bridged diphosphines NUPHOS can be resolved with (S)-BINOL at elevated temperatures to afford diastereopure δ-[(NUPHOS) M{(S)-BINOL}] (M = Pd, Pt). The homochiral Lewis acid complexes δ-[(NUPHOS)M]-[OTf] 2 , generated by protonation of δ-[(NUPHOS)M{(S)-BINOL}] with trifluoromethanesulfonic acid, catalyze the Diels-Alder reaction between acryloyl-N-oxazolidinones and cyclopentadiene to give ee values up to 96%. The corresponding enantiopure dichlorides δ-[(NUPHOS)PtCl 2 ] react with AgClO 4 to form highly efficient catalysts that give good endo/exo selectivities and high endo enantioselectivity.
  • Authors

    Published In

  • Organic Letters  Journal
  • Digital Object Identifier (doi)

    Author List

  • Doherty S; Newman CR; Rath RK; Luo HK; Nieuwenhuyzen M; Knight JG
  • Start Page

  • 3863
  • End Page

  • 3866
  • Volume

  • 5
  • Issue

  • 21