From allylic alcohols to aldols by using iron carbonyls as catalysts: computational study on a novel tandem isomerization-aldolization reaction |
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Authors: | Branchadell Vicenç Crévisy Christophe Grée René |
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Institution: | Departament de Química, Universitat Autònoma de Barcelona, Edifici Cn, 08193 Bellaterra, Spain. vicenc.branchadell@uab.es |
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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. |
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Keywords: | aldol reaction density functional calculations ene reaction enols iron |
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