Enantioselective Nickel-Catalyzed Hydrocyanation using Chiral Phosphine-Phosphite Ligands: Recent Improvements and Insights

Anna Falk, Alberto Cavalieri, Gary S. Nichol, Dieter Vogt, Hans Günther Schmalz

Research output: Contribution to journalArticlepeer-review

Abstract

The asymmetric hydrocyanation of vinylarenes was investigated using hydrogen cyanide (HCN) in the presence of 5 mol% of a catalyst prepared from a phenol-derived chiral phosphine-phosphite ligand and bis(cyclooctadiene)nickel [Ni(cod)2]. The reactions were performed in tetrahydrofuran (THF) at room temperature to give exclusively the branched nitriles with superior enantioselectivities of 88-99% ee for vinylarenes and 74-94% ee for vinylheteroarenes, respectively. Using styrene as a model substrate it was shown that the catalyst loading could be decreased to 0.42 mol% without any loss of selectivity (88% ee). The structure of the pre-catalyst, i.e., a tetrahedral Ni(0)(P,P-chelate)(cod) complex, was proven by X-ray and NMR analysis. Additional insight into the reaction course was gained by monitoring the hydrocyanation of styrene-d8 by means of 2D NMR spectroscopy.

Original languageEnglish
Pages (from-to)3317-3320
Number of pages4
JournalAdvanced Synthesis & Catalysis
Volume357
Issue number14-15
DOIs
Publication statusPublished - 1 Oct 2015

Keywords

  • asymmetric synthesis
  • hydrocyanation
  • hydrogen cyanide (HCN)
  • nickel
  • phosphine-phosphites

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