We have demonstrated that aldehydes react with N-acylphthalimides to form N-phthalimido-O-acyl-N,O-acetals. The process is surprising because it involves a net “insertion” of the aldehyde π bond into the N-acylphthalimide C–N bond. The synthetic utility of this process is enhanced by the variety of N-acylphthalimide substrates that can participate in the reaction. The scope of amenable N-acylphthalimides is fairly broad, but certain substrates (i.e., those lacking an α-hydrogen atom) are unable to form the expected N,O-acetal product. These results suggest that the mechanism may involve a ketene intermediate, which was supported by subsequent deuterium labeling and crossover experiments. Computational studies were carried out to evaluate this hypothesis and gain further mechanistic insight. The scope of competent N-acylphthalimides, experiments and computational studies related to reaction mechanism, along with potential implications of the involvement of a ketene intermediate will be presented.

Mechanistic studies into the reaction of aldehydes with N-acylphthalimides

249th National Meeting (2015)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.