Theoretical studies on cycloaddition reactions between keteniminium cations and olefins

The mechanisms of seven reactions between keteniminium cations and olefins have been theoretically explored at BHandHLYP/6-31G level. It is found that these seven reactions always form a relatively stable hydrogen-bonded type of ion-molecule complex first except for reactions 1d+2a and 1e+2a, which have no hydrogen atom attached to nitrogen atom in keteniminium cations. Some reactions take place via a concerted but unsynchronous mechanism, and the others are stepwise processes. The substituent effects are also studied. The data reveal that the electron-pushing substituents on keteniminium cations disfavor the reaction, and the electron-attracting substituents on keteniminium cations favor the reactions. The substituent effects on ethene are contrary to the former case.