The lithium-catalyzed reaction between an aldehyde and an N-acylphthalimide to form N,O-acetal is described as an insertion reaction, where the aldehyde inserts itself into the N-C bond on the N-acylphthalimide molecule. This research project is a computational determination of the mechanism for this reaction using the M06 density functional theory, the 6-31+G(d,p) basis set, and SMD with acetonitrile as solvent. A number of possible pathways, including ketene formation, acylium ion intermediate formation, and a concerted pathway, were eliminated due to their high energies. This study revealed that phthalimide acts catalytically and reacts with aldehyde to form an Li-alkoxide intermediate (free energy barrier 3.72 kcal/mol ). This species then attacks the N-acylphthalimide, undergoes a conformational change, and then the phthalimide anion leaves to give the product of N,O-acetal.

Computational determination of mechanism for aldehyde insertion into N-acylphthalimides to form N,O-acetals

251st National Meeting (2016)

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