DFT Quest of the Active Species of the Gallium-Mediated Coupling of Methylidenemalonates and Acetylenes.

In this study, three different Ga-containing systems based on GaCl, GaCl, or ionic [Ga(L)][GaCl] (L = methylidenemalonate) complex were screened to elucidate the mechanism, regioselectivity, chemoselectivity, and role of Ga mediator in the reaction between two types of acetylenes (phenylacetylene and but-1-yn-1-ylbenzene) and methylidenemalonates, i.e., the 1,2-zwitterionic precursors that are similar to intermediates derived from donor-acceptor cyclopropanes (DACs). Our DFT calculation results clearly show that the ionic gallium complex [Ga(L)][GaCl] represents the key mediator in the title reaction. After the formation of such a complex, the first reaction step is the nucleophilic addition of phenylacetylene or but-1-yn-1-ylbenzene to [Ga(L)][GaCl], generating an unstable vinyl cation intermediate. In the phenylacetylene system, this vinyl cation intermediate accepts a chlorine atom from [GaCl] to give -configuration intermediate. Then, the above process occurs to other two ligands of the Ga(III) complex to furnish a final product. On the other hand, in the but-1-yn-1-ylbenzene system, the vinyl cation intermediate prefers to undergo Friedel-Crafts (F-C) alkylation to generate a five-membered ring intermediate. This process is repeated on the other two methylidenemalonate ligands, giving rise to a final cyclization product. The distortion/interaction analysis shows that in the nucleophilic addition step the distortion energy of the Ga complex part is the main factor that influences the activation energy. Furthermore, the global reactivity index (GRI) analysis indicates that the Ga-complex model has the highest electrophilicity index ω, thus leading to the lowest energy barrier among three Ga-based models. In addition, DFT results reveal that the regioselectivity (-configuration preference) and chemoselectivity (chloration or F-C alkylation) are mainly controlled by the steric effect rather than the electronic effect. The main findings of the present work provide a new way to analyze and rationalize various Ga-mediated reactions, which might also be extrapolated to organic transformations undergoing in the presence of aluminum and indium complexes.