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Issue 16, 2010
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Quantitative characterization of group electrophilicity and nucleophilicity for intramolecular Diels–Alder reactions

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Abstract

In a previous work (L. R. Domingo, M. J. Aurell, P. Perez and R. Contreras, Tetrahedron 2002, 58, 4417) we proposed that the difference in global electrophilicity index be taken as a measure of the polarity at the transition state in intermolecular Diels–Alder reactions. We herein extend this model to deal with intramolecular Diels–Alder (IMDA) processes. The transferability of the empirical reactivity rules established for the intermolecular DA reactions to the IMDA reactions is discussed. The analysis based on group electrophilicity and nucleophilicity in general fails because having two different reactivity patterns within the same molecule hampers a clean classification of electrophilicity and nucleophilicity of the interacting fragments. We introduce dual philicity indexes E1 and E2 that solve this problem by separating a series of 30 IMDA reactions into two families, namely the diene to dienophile electron flow (DDpF) and the dienophile to diene electron flow (DpDF) processes. The new indexes correctly describe the charge transfer at the transition state and the reaction mechanism expected for the title reactions.

Graphical abstract: Quantitative characterization of group electrophilicity and nucleophilicity for intramolecular Diels–Alder reactions

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Publication details

The article was received on 24 Mar 2010, accepted on 17 May 2010 and first published on 04 Jun 2010


Article type: Paper
DOI: 10.1039/C004628K
Citation: Org. Biomol. Chem., 2010,8, 3678-3683
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    Quantitative characterization of group electrophilicity and nucleophilicity for intramolecular Diels–Alder reactions

    J. Soto-Delgado, L. R. Domingo and R. Contreras, Org. Biomol. Chem., 2010, 8, 3678
    DOI: 10.1039/C004628K

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