BF₃‐CatalyzedMukaiyama aldol reaction of acetaldehyde with 2‐siloxy‐1‐propene

Abstract

The Mukaiyama aldol reaction is a powerful tool for the construction of the carbon-carbon bond and the formation of β-hydroxycarbonyl compounds. In this work, the mechanism of acetaldehyde and 2-siloxy-1-propene both in the absence and presence of the catalyst BF 3 was investigated based on density functional theory. The mechanism includes two major steps: the formation of the carbon-carbon bond and the removal of SiH 3 /BF 2 by water. The energy barrier of the carboncarbon bond formation process in the presence of BF 3 is obviously lower, indicating that BF 3 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 BF 3 . 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.

Neutral Monodentate and Hypervalent Chalcogen Bond Catalysis on the Intramolecular Rauhut‐Currier Reaction of Bis(enones): A DFT Study

“…There are many reactions to construct carbon-carbon bonds, such as Michael addition reaction, Diels-Alder reaction, Friedel-Crafts reaction, Nazarov cyclization reaction, Mukaiyama aldol condensation reaction. [20][21][22][23] The Rauhut-Currier (RC) reaction is also an important basic reaction for the efficient construction of carbon-carbon bonds, [24][25][26] and which can be traced back to a US patent by Rauhut, M and Currier, H [27] in 1963. The RC reaction is the formation of a new carbon-carbon bond between the α-position of an unsaturated olefin and the βposition of another unsaturated alkene under the catalysis of a nucleophilic catalyst.…”