with The Imine and Some of its Derivatives via M06-2X Theory with Basis Set 6-31g(d) and Complete Basis Set
Abstract
The mechanism of cycloaddition reactions of imine and its derivatives with fluoro ketene were studied theoretically using M06-2X/6-31g(d) level of theory and complete basis set extrapolation (CBS). It is found that the reaction takes place through a two-step mechanism: i) the first step is the nucleophilic attack of the electronic pair of the nitrogen atom in imine on the central carbon atom of the carbonyl group in ketene forming a zwitterionic (ZW) intermediate, (ii) the second step represents the rate-limiting step of the reaction, during which an attack occurs by a negative charge on the oxygen in the intermediate compound on the carbon atom a of the iminium. The trans-a-lactam and cis-b-lactam isomers are formed along the endo and exo channels, respectively.
The calculated values of Gibbs free energies by the theoretical methods used in this research indicate that the reactions are more spontaneously thermodynamically for R = CH3, while they are faster in the case of R = NH2 kinetically, thus, the activity of the substituted imines studied can be arranged thermodynamically and kinetically as follows: and , respectively,
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