title: Theoretical studies on the mechanism of acid-promoted hydrolysis of N-formylaziridine in comparison with formamide.
abstract: [reaction: see text] We present an ab initio study of the acid-promoted hydrolysis reaction mechanism of N-formylaziridine in comparison with formamide. Since the rate of amide hydrolysis reactions depends on the formation of the tetrahedral intermediate, we focused our attention mainly on the reactant complex, the tetrahedral intermediate, and the transition state connecting these two stationary points. Geometries were optimized using the density functional theory, and the energetics were refined using ab initio theory including electron correlation. Solvent effects were investigated by using polarizable continuum method calculations. The proton-transfer reaction between the O-protonated and N-protonated amides was investigated. In acidic media, despite that the N-protonated species is more stable than the O-protonated one, it is predicted that both N-protonated and O-protonated pathways compete in the hydrolysis reaction of N-formylaziridine.
authors.affiliation: National Creative Research Initiative Center for Superfunctional Materials, Department of Chemistry, Division of Molecular and Life Sciences, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang 790-784, Korea.
authors.forename: Thanathu Krishnan
authors.initials: TK
authors.lastname: Manojkumar
authors.forename: Seung Bum
authors.initials: SB
authors.lastname: Suh
authors.forename: Kyung Seok
authors.initials: KS
authors.lastname: Oh
authors.forename: Seung Joo
authors.initials: SJ
authors.lastname: Cho
authors.forename: Chunzhi
authors.initials: C
authors.lastname: Cui
authors.forename: Xiang
authors.initials: X
authors.lastname: Zhang
authors.forename: Kwang S
authors.initials: KS
authors.lastname: Kim