Superelectrophilicity in Michael-Type Reactions: Water Addition to 4-Nitrobenzodifuroxan

Sami Lakhdar, Guillaume Berionni, François Terrier

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Kinetic and thermodynamic measurements of the ease of covalent hydration of 4-nitrobenzodifuroxan (NBDF) to give the corresponding hydroxy adduct has been carried out over a large pH range of 0.82-12.23 in aqueous solution. A most important result is that water is the sole efficient nucleophile contributing to the hydration of this peculiar nitroolefin in the pH range 4-8. Based on this finding as well as a p K a H2O value of 2.85 for the complexation process there is no doubt that the electrophilic character of NBDF falls in the domain of superelectrophilicity defined with reference to covalent nucleophilic additions to 4,6-dinitrobenzofuroxan (DNBF; p K a H2O = 3.75) and related heterocycles. This also corresponds to a positioning of NBDF at the top of the electrophilicity scale E introduced by Mayr to describe the feasibility of nucleophilic-electrophilic combinations. Returning to the hydration of the series of activated olefins, it has been possible to expand the domain of reactivity of Michael acceptors by six orders of magnitude, going from benzylidenemalonitrile (p K a H2O = 10.70; E = -9.42) to the para -nitro-substituted benzylidene Meldrum' s acid (p K a H2O = 3.46; E = -5.49). The positioning of these olefins on the p K a scale shows that not only 4-nitrobenzodifuroxan but also the unsubstituted Meldrum's acid are located in the superelectrophilic region.

langueAnglais
Pages3453-3459
Nombre de pages7
journalSynthesis (Germany)
Volume49
Numéro15
Les DOIs
étatPublié - 1 août 2017
Modification externeOui

Empreinte digitale

Hydration
Olefins
Water
Alkenes
Nucleophiles
Acids
Complexation
Thermodynamics
Kinetics
4-nitrobenzodifuroxan

mots-clés

    Citer ceci

    Lakhdar, Sami ; Berionni, Guillaume ; Terrier, François. / Superelectrophilicity in Michael-Type Reactions : Water Addition to 4-Nitrobenzodifuroxan. Dans: Synthesis (Germany). 2017 ; Vol 49, Numéro 15. p. 3453-3459.
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    abstract = "Kinetic and thermodynamic measurements of the ease of covalent hydration of 4-nitrobenzodifuroxan (NBDF) to give the corresponding hydroxy adduct has been carried out over a large pH range of 0.82-12.23 in aqueous solution. A most important result is that water is the sole efficient nucleophile contributing to the hydration of this peculiar nitroolefin in the pH range 4-8. Based on this finding as well as a p K a H2O value of 2.85 for the complexation process there is no doubt that the electrophilic character of NBDF falls in the domain of superelectrophilicity defined with reference to covalent nucleophilic additions to 4,6-dinitrobenzofuroxan (DNBF; p K a H2O = 3.75) and related heterocycles. This also corresponds to a positioning of NBDF at the top of the electrophilicity scale E introduced by Mayr to describe the feasibility of nucleophilic-electrophilic combinations. Returning to the hydration of the series of activated olefins, it has been possible to expand the domain of reactivity of Michael acceptors by six orders of magnitude, going from benzylidenemalonitrile (p K a H2O = 10.70; E = -9.42) to the para -nitro-substituted benzylidene Meldrum' s acid (p K a H2O = 3.46; E = -5.49). The positioning of these olefins on the p K a scale shows that not only 4-nitrobenzodifuroxan but also the unsubstituted Meldrum's acid are located in the superelectrophilic region.",
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    Superelectrophilicity in Michael-Type Reactions : Water Addition to 4-Nitrobenzodifuroxan. / Lakhdar, Sami; Berionni, Guillaume; Terrier, François.

    Dans: Synthesis (Germany), Vol 49, Numéro 15, 01.08.2017, p. 3453-3459.

    Résultats de recherche: Contribution à un journal/une revueArticle

    TY - JOUR

    T1 - Superelectrophilicity in Michael-Type Reactions

    T2 - Synthesis

    AU - Lakhdar, Sami

    AU - Berionni, Guillaume

    AU - Terrier, François

    PY - 2017/8/1

    Y1 - 2017/8/1

    N2 - Kinetic and thermodynamic measurements of the ease of covalent hydration of 4-nitrobenzodifuroxan (NBDF) to give the corresponding hydroxy adduct has been carried out over a large pH range of 0.82-12.23 in aqueous solution. A most important result is that water is the sole efficient nucleophile contributing to the hydration of this peculiar nitroolefin in the pH range 4-8. Based on this finding as well as a p K a H2O value of 2.85 for the complexation process there is no doubt that the electrophilic character of NBDF falls in the domain of superelectrophilicity defined with reference to covalent nucleophilic additions to 4,6-dinitrobenzofuroxan (DNBF; p K a H2O = 3.75) and related heterocycles. This also corresponds to a positioning of NBDF at the top of the electrophilicity scale E introduced by Mayr to describe the feasibility of nucleophilic-electrophilic combinations. Returning to the hydration of the series of activated olefins, it has been possible to expand the domain of reactivity of Michael acceptors by six orders of magnitude, going from benzylidenemalonitrile (p K a H2O = 10.70; E = -9.42) to the para -nitro-substituted benzylidene Meldrum' s acid (p K a H2O = 3.46; E = -5.49). The positioning of these olefins on the p K a scale shows that not only 4-nitrobenzodifuroxan but also the unsubstituted Meldrum's acid are located in the superelectrophilic region.

    AB - Kinetic and thermodynamic measurements of the ease of covalent hydration of 4-nitrobenzodifuroxan (NBDF) to give the corresponding hydroxy adduct has been carried out over a large pH range of 0.82-12.23 in aqueous solution. A most important result is that water is the sole efficient nucleophile contributing to the hydration of this peculiar nitroolefin in the pH range 4-8. Based on this finding as well as a p K a H2O value of 2.85 for the complexation process there is no doubt that the electrophilic character of NBDF falls in the domain of superelectrophilicity defined with reference to covalent nucleophilic additions to 4,6-dinitrobenzofuroxan (DNBF; p K a H2O = 3.75) and related heterocycles. This also corresponds to a positioning of NBDF at the top of the electrophilicity scale E introduced by Mayr to describe the feasibility of nucleophilic-electrophilic combinations. Returning to the hydration of the series of activated olefins, it has been possible to expand the domain of reactivity of Michael acceptors by six orders of magnitude, going from benzylidenemalonitrile (p K a H2O = 10.70; E = -9.42) to the para -nitro-substituted benzylidene Meldrum' s acid (p K a H2O = 3.46; E = -5.49). The positioning of these olefins on the p K a scale shows that not only 4-nitrobenzodifuroxan but also the unsubstituted Meldrum's acid are located in the superelectrophilic region.

    KW - covalent hydration

    KW - electrophilicity scales

    KW - kinetics

    KW - Michael additions

    KW - nitroolefins

    KW - superelectrophiles

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