Theoretical Study of Acid-Catalyzed Hydrolysis of Epoxides

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-04, Vol.114 (15), p.5187-5194
• Main Authors: Muniz Filho, Raimundo Clecio Dantas, Sousa, Samuel Anderson Alves de, Pereira, Flávia da Silva, Ferreira, Márcia Miguel Castro
• Format: Article
• Language: English
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp9106316

A theoretical study of propylene oxide acid-catalyzed hydrolysis was performed by investigation of the SN1 and SN2-like mechanisms. By using chemometric tools, hierarchical cluster analysis (HCA), and principal component analysis (PCA), the MP2/6-311++G** level of theory was selected from HF, MP2, and DFT as the best method to describe the geometry of the basic skeleton (oxirane). At this level of theory, geometry optimizations, vibrational frequencies, intrinsic reaction coordinate (IRC), and other thermodynamic calculations have shown that the borderline SN2 mechanism is more favorable than pure SN2 and SN1 mechanisms in the gas phase. In the SN1 mechanism, the existence of the typical carbocation was not observed, and furthermore, the possibility of epoxide conversion to a protonated aldehyde was indicated, even in the presence of a water molecule (nucleophile). The Chelpg charge distribution of the reactants, steric hindrance, synchronous bond breaking−formation and trajectory angle of nucleophilic attack are discussed for pure and borderline SN2 mechanisms. Solvation effect calculations indicate that the pure SN2 mechanism is more favorable than borderline SN2 and SN1 mechanisms. This is discussed in terms of hydrogen bond formation.