The theoretical chemical calculations clarify the mechanism of beta-alkylation of 1-phenylethanol with benzyl alcohol catalyzed by iron(ii) acetylacetonate methods.

Iron(ii) acetylacetonate was suggested to be a better catalyst of the β-alkylation of 1-phenylethanol with benzyl alcohol to form 1,3-diphenyl-1-propanol. DFT calculations have been performed to study the internal mechanism, the structures of intermediates and transition states, and the exchange of electronic density in detail. The energetic results show that this β-alkylation reaction proceeds the hydrogen autotransfer mechanism and the catalytic cycle includes three sequential stages: (1) alcohol oxidation to produce aldehyde associated with hydride anion transfer, (2) cross-aldol condensation to form a chalcone and (3) chalcone reduction with multi-step hydrogenation. In order to study whether the only by-product, water, has clearly influenced the reaction, eight catalyst hydrogenation pathways and four catalyst dehydrogenation pathways have been studied. We are delighted to find that the presence of the only by-product, water, can significantly increase the reduction energy barrier of dihydrochalcone. The energy barrier of the catalyst's hydrogenation is less than 6 kcal mol. Our calculation results are fundamentally coincident with the experimental detections, and suggest that the crossing-coupling reaction occurs through a reliable mechanism. Two dihydrochalcone catalysts were designed on the basis of how the β-alkylation reaction proceeds.