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Cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine: Studies in regio- and stereoselectivity

Cycloadditionen von Nitriloxiden und Nitronen an 4,4-Methylen-1-methylpiperidin: Untersuchungen zur Regio- und Stereoselektivität

  • Organische Chemie Und Biochemie
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Summary

A series of spiro-substituted isoxazole derivatives were synthesized by 1,3-dipolar cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine. Since nmr studies confirmed that only one regioisomer was formed selectively, semi-empirical quantum mechanical methods (AM1) were used to rationalize this regiochemical preference via calculation and inspection of HOMO-LUMO-energy and coefficients. X-ray structure analysis carried out for one of these products showed the occurrence of only one stereoisomer, explicable by comparing AM1-calculated ΔH f -values of all possible cycloadducts.

Zusammenfassung

Eine Reihe von spiro-substituierten Isoxazolderivaten wurden durch 1,3-dipolare Cycloaddition von Nitriloxiden und Nitronen an 4,4-Methylen-1-methylpiperidin erhalten. Da NMR-Studien ergaben, daß dabei nur eine der beiden denkbaren regioisomeren Strukturen entsteht, wurde versucht, diese regiochemische Preferenz durch Berechnung und Vergleich von aus halb-empirischen quantenmechanischen Methoden (AM1) ermittelten HOMO-LUMO-Energien und Koeffizienten zu erklären. Zusätzlich wurde an einem dieser Produkte dessen Stereochemie mittels Röntgenstrukturanalyse als einheitlich festgestellt, interpretierbar durch Vergleich der AM1-ermittelten ΔH f -Werte der in Frage kommenden Cycloaddukte.

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Authors and Affiliations

  1. Institute of Organic Chemistry, Technical University Vienna, A-1060, Vienna, Austria

    F. Sauter, J. Fröhlich & Y. Feng

  2. Department of Organic Chemistry, Slovak Technical University, SQ-812 37, Bratislava, Slovakia

    L. Fišera

  3. Institute of Chemistry, Comenius University, SQ-842 15, Bratislava, Slovakia

    P. Ertl

  4. Institute of Crystallography, Mineralogy and Structure Chemistry, Technical University Vienna, A-1060, Vienna, Austria

    K. Mereiter

Authors
  1. L. Fišera
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  2. F. Sauter
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  3. J. Fröhlich
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  4. Y. Feng
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  5. P. Ertl
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  6. K. Mereiter
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Additional information

Part XXXI in the series 1,3-Dipolar Cycloaddition on Heterocycles. Part XXX [Ref. 5]

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Fišera, L., Sauter, F., Fröhlich, J. et al. Cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine: Studies in regio- and stereoselectivity. Monatsh Chem 125, 553–563 (1994). https://doi.org/10.1007/BF00811848

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  • DOI: https://doi.org/10.1007/BF00811848

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