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A full theoretical study of the reaction between a novel type of ylide, i.e. nitrone ylides, and alkenes has been carried out. Both concerted and polar stepwise mechanisms have been considered. Only the zwitterionic mechanism predicts correctly the experimentally observed adducts. Depending on the level of theory, the mechanism moves from concerted to polar stepwise, as demonstrated by the corresponding IRC analyses. The regio- and stereoselectivity of the reaction is well explained for both mono- and disubstituted alkenes. In the case of methyl acrylate a pathway leading to the two diastereoisomers obtained experimentally is predicted. For methyl fumarate a stereospecific mechanism is predicted as a consequence of a C-H···O═C interaction present in a Li-tricoordinated transition structure. The stereospecificity in the reaction with methyl maleate comes from a less hindered coordination around the lithium atom. Calculations with B3LYP and M06-2X functionals indicate that only the latter provides energy values in good agreement with experimental findings.

Theoretical Elucidation of the Mechanism of the Cycloaddition between Nitrone Ylides and Electron-Deficient Alkenes