Nitrile modulated-Ni(0) phosphines in trans-selective phenylpropenoids isomerization: An allylic route by a regular η1-N(end-on) or an alkyl route via a flipped-nitrile?

Leo Saputra, Arifin, Nunik Gustini, Novitasari Sinambela, Nova Pratiwi Indriyani, Aditya Wibawa Sakti, Ubed Sonai Fahruddin Arrozi, Muhamad A. Martoprawiro, Aep Patah, Yessi Permana*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Acetonitrile has been widely viewed as a weakly coordinating solvent in metal-catalyzed reactions. Evidence is presented herein that it worked as an actor ligand in nickel-catalyzed stereoselective isomerizations of eugenol, methyl eugenol, estragole, and allylphenol, with trans-isomerized products of ≥95%. Nickel(0)(nitrile)phosphines were generated in situ from Ni(II) salt in the presence of phosphines, Zn, and nitrile with Ni/phosphines/Zn/nitrile mole ratio as low as 1:2:1:1. The isomerization of eugenol gave trans-isoeugenol of >97% in 30 min at r.t. with Ni turnover frequency (TOF) up to 1,116 h−1 and the activation energy of 61 kJ·mol−1. High selectivity of trans-isoeugenol was retained in continuous and multi-gram trials. Density functional theory (DFT)/PBE0-D3 calculations rationalized the possible formation of nickel hydride (i.e., Ni(H)(η1-CH2CN)(phosphine) complex) from η1-N(end-on)-Ni complex. This nitrile modulated-Ni(0) complex indicated the complex followed an alkyl-type isomerization, instead of a conventional allylic-type one.

Original languageEnglish
Article number112768
JournalMolecular Catalysis
Volume533
DOIs
Publication statusPublished - 2022 Dec

Keywords

  • Alkyl-type isomerizations
  • DFT/PBE0-D3
  • Flipped-nitrile
  • Nickel(nitrile)(phosphines)
  • Phenylpropenoids isomerization

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

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