Understanding the Reactivity of C-Cyclopropyl-N-Methylnitrone Participating in [3+2] Cycloaddition Reactions Towards Styrene with a Molecular Electron Density Theory Perspective
DOI:
https://doi.org/10.29356/jmcs.v65i1.1437Keywords:
Electron localization function, isoxazolidines, [3 2] cycloaddition reactions, molecular electron density theoryAbstract
Abstract. The [3+2] cycloaddition (32CA) reactions of C-cyclopropyl-N-methylnitrone 1 with styrene 2 have been studied within molecular electron density theory (MEDT) at the B3LYP/6-311++G(d,p) level of theory. These zwitterionic type 32CA reactions occur through a one-step mechanism. The 32CA reactions undergo four stereo- and regioisomeric reaction paths to form four different products, 3, 4, 5 and 6. Analysis of the conceptual density functional theory (CDFT) indices predict the global electronic flux from the strong nucleophilic nitrone 1 to the styrene 2. These 32CA reactions are endergonic with reactions Gibbs free energies between 2.83 and 7.39 kcal.mol-1 in the gas phase. The 32CA reaction leading to the formation of cycloadduct 3 presents the lowest activation enthalpy than the other paths due to a slightly increase in polar character evident from the global electron density transfer (GEDT) at the transition states and along the reaction path. The bonding evolution theory (BET) study suggests that these 32CA reactions occur through the coupling of pseudoradical centers and the formation of new C-C and C-O covalent bonds has not been started in the transition states.
Resumen. Las reacciones de cicloadición [3+2], denotadas como 32CA, entre C-ciclopropil-N-metilnitrona 1y estireno 2se estudian mediante la teoría de la densidad electrónica molecular (MEDT) utilizando el nivel de teoría B3LYP/6-311++G(d,p). Estas reacciones 32CA de tipo zwiteriónicasse llevan por un mecanimso de un paso. Las reacciones 32CA ocurren a través de cuatro caminos estereo y regioisoméricos de reacción formando cuatro diferentes productos 3, 4, 5y 6. El análisis de los índices de la teoría conceptual de funcionales de la densidad (CDFT) predice un flujo electrónico global de la nitrona 1, un nucleófilo fuerte, al estireno 2. En fase gaseosa,estas reacciones 32CA son endergónicas con energías libres de Gibbs entre 2.83 y 7.39 kcal.mol-1. La reacción 32CA que lleva a la formación del cicloaducto 3tiene la menor entalpía de activación de las cuatro consideradas y esto se debe a un ligero incremento en el carácter polar que es evidente con la transferencia global de densidad electrónica (GEDT) en los estados de transición y a lo largo de los caminos de reacción. El esudio mediante la teoría de evolución del enlace (BET) sugiere que estas reacciones 32CA ocurren mediante el acoplamiento de centros pseudoradicalesy la formación de nuevos enlaces covalentes C-C y C-O que no han iniciado en el estado de transición.
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