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Regioselectivity in the 1,3-dipolar cycloaddition of nitrile oxides to N-(3,5-dichlorophenyl)itaconimide

Regioselektivität bei der 1,3-dipolaren Cycloaddition von Nitriloxiden mit N-(3,5-Dichlorphenyl)itaconimid

  • Organische Chemie Und Biochemie
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Summary

The regioselectivity of the nitrile oxide cycloaddition with 3,3-methylene-1-(3,5-dichlorophenyl)-2,5-pyrrolidindione (1) is discussed. Arylnitrile oxides add regioselectively to the carboncarbon double bond of1, giving exclusively spiro-isoxazolines3a–k, whereas acetonitrile oxide gives both adducts3l and4l. AM1 calculations of the reactants and cycloadducts were performed, the regiochemistry of the cycloaddition seems to be controlled by steric effects. Reduction of3a with NaBH4 in the presence of magnesium perchlorate at −20 °C was regio-and stereoselective to yield the hydroxylactams9a and10a, whereas hydroxymethylisoxazoline14a was obtained in the absence of Mg(ClO4)2.

Zusammenfassung

Es wird die Regioselektivität der Cycloaddition von Nitriloxiden mit 3,3-Methylen-1-(3,5-Dichlorphenyl)-2,5-pyrrolidinon (1) diskutiert. Arylnitriloxide addieren regioselektiv an die Kohlenstoff-Kohlenstoff-Doppelbindung von1 unter ausschließlicher Bildung der Spiroisoxazoline3a–k, währenddessen Acetonitriloxid beide Addukte3l und4l ergibt. AM1-Rechnungen der Reaktanden und der Cycloaddukte sprechen dafür, daß der regiochemische Verlauf der Cycloaddition durch sterische Effekte bewirkt wird. Reduktion von3a mit NaBH4 in Gegenwart von Magnesiumperchlorat bei −20 °C ergab in einer regio- und stereoselektiven Reaktion die Hydroxylaktame9a und10a, in Abwesenheit von Mg(ClO4)2 wurde Hydroxymethylisoxazolin14a erhalten.

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Authors and Affiliations

  1. Department of Organic Chemistry, Slovak Technical University, SK-81237, Bratislava, Slovakia

    Ľ. Fišera & M. Konopíková

  2. Institute of Chemistry, Comenius University, SK-84215, Bratislava, Slovakia

    P. Ertl

  3. Central Laboratory of Chemical Techniques, Slovak Technical University, SK-81237, Bratislava, Slovakia

    N. Prónayová

Authors
  1. Ľ. Fišera
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  2. M. Konopíková
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  3. P. Ertl
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  4. N. Prónayová
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Additional information

Part XXX in the series 1,3-Dipolar Cycloaddition on Heterocycles. Part XXIX [27]

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Fišera, Ľ., Konopíková, M., Ertl, P. et al. Regioselectivity in the 1,3-dipolar cycloaddition of nitrile oxides to N-(3,5-dichlorophenyl)itaconimide. Monatsh Chem 125, 301–312 (1994). https://doi.org/10.1007/BF00811316

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  • DOI: https://doi.org/10.1007/BF00811316

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