On the 1,3-dipolar cycloaddition reactions of indenone with N-N-C dipoles: density functional theory calculations
Abraham F Jalbout1, Z Jiang, H Abou-Rachid
1Departamento de Química Orgánica, Grupo de Modelización y Diseño Molecular, Campus Fuentenueva, Universidad de Granada, 18071 Granada, Spain. ajalbout@ejmaps.org
Abstract:
Density functional theory (DFT) calculations at the B3LYP/6-311G* theoretical level have been performed to study the 1,3-dipolar cycloaddition (1,3-DC) reactions between indenone (1) and different 1,3-dipoles (diazomethane and N-methyl C-methoxy carbonyl nitrilimine, compounds 2 and 3, respectively). The geometrical and energetic properties were analysed for the different reactives, transition states and cycloadducts formed (compounds 4-11). The reactions proceed in the gas-phase by an asynchronous concerted mechanism, yielding different regiochemistry dependent on the 1,3-dipole chosen, although with dipole 3 some degree of synchrony was found in the formation of cycloadduct 5. The 1,3-DC between 1 and 3 was regioselective, being the cycloadduct 11 favoured against 9. The NMR chemical shift parameters (GIAO method) were also calculated for the reactives and cycloadducts.
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