Monatshefte für Chemie / Chemical Monthly

, Volume 122, Issue 11, pp 977–985 | Cite as

Regio- and stereoselectivity in the 1,3-dipolar cycloaddition of C,N-diarylnitrones to 3,3-methylene-5,5-dimethyl-2-pyrrolidinone

  • Peter Oravec
  • Ľubor Fišera
  • Igor Goljer
  • Peter Ertl
Organische Chemie Und Biochemie

Summary

Regio- and stereoselectivity of the nitrone cycloaddition with 3,3-methylene-5,5-dimethyl-2-pyrrolidinone ((1) is discussed. Nitrones react regioselectively with1 to give a mixture of diastereoisomeric spiro-cycloadducts3 and4, in which3 always dominates. Both3 and4 result from the approach which binds the carbon of the nitrone with the exocyclic carbon of1 and the oxygen to the spiro carbon. The structure and steric configuration of the adducts have been assigned on the basis of1H- and13C-NMR spectroscopy, mainly by nuclear Overhauser effect difference spectroscopy. AM1 calculations of the reactants were performed, the regio- and stereochemistry of the cycloaddition seems to be controlled by steric effects.

Keywords

1,3-Dipolar cycloaddition of nitrones 3,3-Methylene-5,5-dimethyl-2-pyrrolidinone Regio- and stereoselectivity of 1,3-dipolar cycloaddition 

Regio- und Stereoselektivität bei der 1,3-dipolaren Cycloaddition von C,N-Diarylnitronen an 3,3-Methylen-5,5-dimethyl-2-pyrolidinon

Zusammenfassung

Es wird die Regio- und Stereoselektivität der Cycloaddition von Nitronen an 3,3-Methylen-5,5-dimethyl-2-pyrolidinon (1) diskutiert. Nitrone reagieren mit1 regioselektiv zu einer Mischung von diastereomeren Spirocycloaddukten3 und4, wobei3 stets dominierend ist. Sowohl3 als auch4 resultieren aus der gleichen Reaktionsanordnung unter Bindung des Nitron-Kohlenstoffatoms an das exocyclische Kohlenstoffatom von1 und des Sauerstoffatoms an den Spiro-Kohlenstoff. Die Stereochemie der Addukte wurde auf Basis von1H- und13C-NMR-Spektroskopie, insbesondere aus Differenz-Nuclear-Overhauser-Messungen, abgeleitet. Es wurden auch AM1-Rechnungen durchgeführt. Die Regio- und Stereochemie der Cycloaddition scheint von sterischen Effekten bestimmt zu sein.

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Copyright information

© Springer-Verlag 1991

Authors and Affiliations

  • Peter Oravec
    • 4
  • Ľubor Fišera
    • 1
  • Igor Goljer
    • 2
  • Peter Ertl
    • 3
  1. 1.Department of Organic ChemistrySlovak Technical UniversityBratislavaCzechoslovakia
  2. 2.Central Laboratory of Chemical TechniquesSlovak Technical UniversityBratislavaCzechoslovakia
  3. 3.Chemical InstituteComenius UniversityBratislavaCzechoslovakia
  4. 4.Department of Biochemistry, Faculty of SciencesP. J. Safarik UniversityKošiceCzechoslovakia

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