Abstract
The [3+2] cycloaddition (32CA) reactions of cyclic azomethine ylides with a series of acetylene derivatives have been studied within the Molecular Electron Density Theory (MEDT). Analysis of the Conceptual DFT indices allows the characterisation of the ambiphilic character of these cyclic AYs, thus participating as strong electrophiles and strong nucleophiles in polar 32CA reactions. The activation enthalpies associated with the 32CA reactions of these cyclic AYs are found in reasonable agreement with the experimental outcomes. These reactions proceed through a one‐step mechanism. The 32CA reactions with 1‐dimethylamino‐1‐propyne and dimethyl acetylenedicarboxylate take place through highly asynchronous polar transition states (TSs). On the other hand, the strain present in cyclooctyne allows explaining its participation in a non‐polar 32CA reaction via a synchronous TS. The present MEDT study allows establishing that the substitution in these cyclic AYs changes their parent pseudodiradical‐type reactivity to the zwitterionic‐type one.
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