Theoretical Investigation On The Mechanism Of Ferrocenecarboxaldehyde-catalyzed Direct β-Alkylation Of 1-phenylethanol With Benzyl Alcohol

As a kind of cheap and free of contamination metal, iron has a wide range of use in the experimental studies and industrial preparation, compounds containing iron in organic synthesis catalyzed have a particularly important role. In this artical, we performed the detailed mechanism investigation for 1-phenylethanol with benzyl alcohol catalyzed by ferrocenecarboxaldehyde with the help of sodium hydroxide in p-xylene solution. Without sacrificial agent(hydrogen acceptors or hydrogen donors) and complex nitrogen or phosphorus ligands are the biggest characteristic of this system and reduce the pollution of the reaction. Our theoretical mechanism well explain the coupling reaction process at the same time, our calculations make a reasonable explanation for the experimental observations of the catalytic system. The main results of this work can be summarized as follows:The structures of intermediates and transition states, the exchange of electronic density and the reaction potential energy surface are computed in detail. In general, the catalyzed reaction is consists of three steps: hydride transfer step with the electron transfer, crossing-aldol condensation step, and the olefin reduction step. Hydride transfer is the speed control step with the highest energy barrier(about 32 kcal/mol). Our calculation results are fundamentally coincident with the experimental detections, and manifest the crossing-coupling reaction occurs through a reliable mechanism.