Details of the Mechanism of the Asymmetric Transfer Hydrogenation of Acetophenone Using the Amine(imine)diphosphine Iron Precatalyst: The Base Effect and the Enantiodetermining Step

Weiwei Zuo, Demyan E. Prokopchuk, Alan J. Lough, Robert H. Morris

Research output: Contribution to journalArticle

38 Scopus citations

Abstract

The excellent ketone asymmetric transfer hydrogenation (ATH) systems using the precatalysts (S,S)-trans-[FeCl(CO)(PPh2CH2CH2NHCHPhCHPhNCHCH2PAr2)]BPh4 (Ar = Ph (1), p-tolyl (2)) have a fascinating dependence of activity on the base concentration, which is investigated here. The reaction of complex 1 or 2 with 1 equiv of the strong base potassium tert-butoxide in THF for 2-7 days produces the neutral amine(ene-amido) complexes [FeCl(CO)(PPh2CH2CH2NHCHPhCHPhNCHCHPAr2)] (8 and 9). These monodeprotonated complexes have been completely characterized by NMR, EA, and FT-IR spectroscopy and mass spectrometry, and the structure of 9 has been further confirmed by single-crystal X-ray diffraction to reveal a structure with the NH and FeCl bonds parallel and the proton and chloride ligands next to each other. The structures of 8 and 9 and their 1H NMR patterns are similar to those of the active catalyst for the ATH of ketones that is postulated to have NH and FeH bonds parallel with the protonic and hydridic hydrogens adjacent. Identical key nuclear Overhauser effect (NOE) correlations in both 8 and the hydrido complex provide further evidence for the postulated structure of the amine iron hydride intermediate. The catalyst system is not active for the transfer hydrogenation of acetophenone, unless greater than 2 equiv of base is added to activate the precatalyst. The addition of base (up to 8 equiv per iron) increases the reaction rate, while a further increase of the base concentration shows a reduction of activity. The loss of activity with less than 2 equiv of base results from a side reaction of the active amido(ene-amido) complexes with 2-propanol to form an inactive neutral bis(amido) iron complex, which was characterized by NMR spectroscopy. Structural evidence for this was provided by the X-ray crystal structure determination of an analogous bis(amino) iron(II) complex, generated from the reaction of the amine(ene-amido) iron complex with methanol in C6D6 in the presence of BF4-. The presence of excess base prevents this side reaction, thereby favoring the reaction which forms the active amine iron hydride species that is in the catalytic cycle. The structure of the transition state for the reaction of the amine hydrido iron catalyst with acetophenone has been successfully modeled using density functional theory (DFT) calculations. The (R) configuration of the product 1-phenylethanol is induced by the position of the phenyl groups on the catalyst and a π-π stabilizing interaction between the aryl ring on the ketone and the ene-amido moiety on the ligand.

Original languageEnglish (US)
Pages (from-to)301-314
Number of pages14
JournalACS Catalysis
Volume6
Issue number1
DOIs
StatePublished - Jan 4 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • amido ligand
  • asymmetric transfer hydrogenation
  • iron catalyst
  • ketone reduction
  • mechanism

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