Selectivities of multicomponent [4 + 2]/[3 + 2] cycloadditions of 3-nitroindole with substituted alkenes: a DFT analysis. - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Organic Chemistry Année : 2013

Selectivities of multicomponent [4 + 2]/[3 + 2] cycloadditions of 3-nitroindole with substituted alkenes: a DFT analysis.

Résumé

The chemo-, regio-, and stereoselectivities of multicomponent [4 + 2]/[3 + 2] domino cycloaddition reactions involving nitroindole derivatives with vinylethers and acrylates are studied computationnally and compared to experimental results. In this process, the nitroarene first reacts as an electron-deficient heterodiene with the electron-rich alkene following an inverse electron-demand [4 + 2] process, leading to a nitronate intermediate in a fully selective way. This intermediate exclusively interacts, in a second step, with the electron-deficient alkene and undergoes a chemo- and regioselective [3 + 2] cycloaddition. The density functional theory calculations reported in this Article fully account for the selectivities observed experimentally. Electronic displacements along the reaction path are examined using a topological analysis of the electron-localization function (ELF). The first [4 + 2] reaction follows a classical concerted, although asynchronous process, which is reliably described by the frontier molecular-orbital (FMO) model. In contrast, the electronic displacements observed during the second [3 + 2] step are unexpected, involving an electron donation by the electron-deficient reaction partner.

Domaines

Chimie organique
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Dates et versions

hal-00996917 , version 1 (27-05-2014)

Identifiants

Citer

Hélène Gérard, Isabelle Chataigner. Selectivities of multicomponent [4 + 2]/[3 + 2] cycloadditions of 3-nitroindole with substituted alkenes: a DFT analysis.. Journal of Organic Chemistry, 2013, 78 (18), pp.9233-9242. ⟨10.1021/jo401482b⟩. ⟨hal-00996917⟩
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