BINAP(O) Induces Enantioselectivity

  • Author: Lois O'Leary
  • Published Date: 31 December 2012
  • Source / Publisher: ChemCatChem/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
thumbnail image: BINAP(O) Induces Enantioselectivity

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The Mizoroki-Heck reaction is widely used for the enantioselective synthesis of sterically strained molecules with tertiary or quaternary carbon centers. The chiral phosphine ligand 2,2,'-bis(diphenylphosphino)-1,1,'-binaphthyl (BINAP) has been the running favorite for this reaction. However, in desymmetrizing Mizoroki-Heck cyclizations, the use of BINAP yields nearly racemic material. For these reactions, Martin Oestreich and Thorsten H. Wöste, Technische Universität Berlin, Germany, have uncovered the enantioselectivity of BINAP(O) as a palladium ligand, which contains an oxidized phosphine center P=O.

BINAP(O) induced unprecedented enantiocontrol. Up to 18-fold increases in enantioselectivity with yields of up to 94 % were achieved for the cyclizations with BINAP(O) as a chiral ligand compared to those with the conventional BINAP ligand.

BINAP(O) acts as a hemilabile chiral ligand, allowing for reversible coordination of the weak donor P=O group. As a bidentate ligand, BINAP(O) mediates the equilibration of diastereomeric alkene-palladium(II) complexes. Its subsequent dissociation from the palladium(II) atom renders it monodentate, which is known to be advantageous to the ring-closing reaction. These results have great implications for the scope of enantioselective cyclization reactions, putting BINAP(O) on the map!

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