Nickel-Catalyzed Stereodivergent Synthesis of E- and Z-Alkenes by Hydrogenation of Alkynes

Kathiravan Murugesan, Charles Beromeo Bheeter, Pim R. Linnebank, Anke Spannenberg, Joost N.H. Reek, Rajenahally V. Jagadeesh, Matthias Beller

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61 Scopus citations

Abstract

A convenient protocol for stereodivergent hydrogenation of alkynes to E- and Z-alkenes by using nickel catalysts was developed. Simple Ni(NO3)2⋅6 H2O as a catalyst precursor formed active nanoparticles, which were effective for the semihydrogenation of several alkynes with high selectivity for the Z-alkene (Z/E>99:1). Upon addition of specific multidentate ligands (triphos, tetraphos), the resulting molecular catalysts were highly selective for the E-alkene products (E/Z>99:1). Mechanistic studies revealed that the Z-alkene-selective catalyst was heterogeneous whereas the E-alkene-selective catalyst was homogeneous. In the latter case, the alkyne was first hydrogenated to a Z-alkene, which was subsequently isomerized to the E-alkene. This proposal was supported by density functional theory calculations. This synthetic methodology was shown to be generally applicable in >40 examples and scalable to multigram-scale experiments.

Original languageEnglish
Pages (from-to)3363-3369
Number of pages7
JournalChemSusChem
Volume12
Issue number14
DOIs
StatePublished - 19 Jul 2019
Externally publishedYes

Keywords

  • alkenes
  • alkynes
  • hydrogenation
  • nickel
  • stereoselectivity

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