BF3-Catalyzed Mukaiyama aldol reaction of acetaldehyde with 2-siloxy-1-propene

The Mukaiyama aldol reaction is a powerful tool for the construction of the carbon-carbon bond and the formation of beta-hydroxycarbonyl compounds. In this work, the mechanism of acetaldehyde and 2-siloxy-1-propene both in the absence and presence of the catalyst BF3 was investigated based on density functional theory. The mechanism includes two major steps: the formation of the carbon-carbon bond and the removal of SiH3/BF2 by water. The energy barrier of the carbon-carbon bond formation process in the presence of BF3 is obviously lower, indicating that BF3 is a good catalyst for this reaction. In terms of molecular configuration, the different tensions between the five-membered-ring and six-membered-ring can be considered as the possible reason for the catalytic effect of BF3. In terms of charge transfer, the charges of natural population analysis in the carbon atom of the carbonyl group in acetaldehyde becomes more positive, which is easier to attack by nucleophiles and promote the nucleophilic process.

Automated summary

The mechanism of the Mukaiyama aldol reaction was investigated using density functional theory, revealing that BF3 serves as a good catalyst for the reaction by lowering the energy barrier of the carbon-carbon bond formation process. The tension between different ring structures and the charge transfer in acetaldehyde may contribute to the catalytic effect of BF3.