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Issue 48, 2008
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Rationalization of Diels–Alder reactions through the use of the dual reactivity descriptor Δf(r)

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Abstract

In this work, the dual descriptor of chemical reactivity, an electronic density-based index, is used to study both the regioselectivity and the stereoselectivity of Diels–Alder reactions. The descriptor has been designed to simultaneously delineate the nucleophilic and electrophilic sites within a molecule. Subsequent pairing between the nucleophilic and electrophilic regions of the reagents predicts the major adducts in all cases studied. Specifically, the descriptor predicts the generation of a ortho-regioisomer when a diene monosubstitued at position 1 by an Electron Donating Group (EDG)/ Electron Withdrawing Group (EWG), reacts with a dienophile monosubtituted by an EWG/EDG. Under the same conditions, if the diene is monosubstituted by either an EWG or an EDG at position 2, formation of the para-oriented adduct is predicted. This approach also provides insight into the stereoselectivity. For example, secondary interactions between the non-reactive regions of the reactants explain why the endo stereoisomer is preferred.

Graphical abstract: Rationalization of Diels–Alder reactions through the use of the dual reactivity descriptor Δf(r)

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Publication details

The article was received on 18 Jun 2008, accepted on 17 Sep 2008 and first published on 23 Oct 2008


Article type: Paper
DOI: 10.1039/B810343G
Citation: Phys. Chem. Chem. Phys., 2008,10, 7239-7246

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    Rationalization of Diels–Alder reactions through the use of the dual reactivity descriptor Δf(r)

    C. Morell, P. W. Ayers, A. Grand, S. Gutiérrez-Oliva and A. Toro-Labbé, Phys. Chem. Chem. Phys., 2008, 10, 7239
    DOI: 10.1039/B810343G

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