From allylic alcohols to aldols by using iron carbonyls as catalysts: Computational study on a novel tandem isomerization-aldolization reaction

Vicenç Branchadell, Christophe Crévisy, René Grée

Research output: Contribution to journalArticleResearchpeer-review

33 Citations (Scopus)

Abstract

The tandem isomerization-aldolization reaction between allyl alcohol and formaldehyde mediated by [Fe(CO)3] was studied with the density functional B3LYP method. Starting from the key [(enol)Fe(CO)3] complex, several reaction paths for the reaction with formaldehyde were explored. The results show that the most favorable reaction path involves first an enol/allyl alcohol ligand-exchange process followed by direct condensation of formaldehyde with the free enol. During this process, formation of the new C-C bond takes place simultaneously with a proton transfer between the enol and the aldehyde. Therefore, the role of [Fe(CO)3] is to catalyze the allyl alcohol to enol isomerization affording the free enol, which adds to the aldehyde in a carbonyl-ene type reaction. Similar results were obtained for the reaction between allyl alcohol and acetaldehyde.
Original languageEnglish
Pages (from-to)5795-5803
JournalChemistry - A European Journal
Volume10
Issue number22
DOIs
Publication statusPublished - 5 Nov 2004

Keywords

  • Aldol reaction
  • Density functional calculations
  • Ene reaction
  • Enols
  • Iron

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