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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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Synthesis of functionalized pyrazole derivatives by regioselective [3+2] cycloadditions of N-Boc-α-amino acid-derived ynones

Eva Pušavec Kirar
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
  • Other articles by this author:
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/ Uroš Grošelj
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
  • Other articles by this author:
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/ Amalija Golobič
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
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/ Franc Požgan
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
  • EN-FIST, Centre of Excellence, Trg Osvobodilne fronte 13, 1000 Ljubljana, Slovenia
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Sebastijan Ričko
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Bogdan Štefane
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
  • EN-FIST, Centre of Excellence, Trg Osvobodilne fronte 13, 1000 Ljubljana, Slovenia
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Jurij Svete
  • Corresponding author
  • Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
  • EN-FIST, Centre of Excellence, Trg Osvobodilne fronte 13, 1000 Ljubljana, Slovenia, Fax: +386-12419-144
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
Published Online: 2018-06-08 | DOI: https://doi.org/10.1515/znb-2018-0013

Abstract

[3+2] cycloadditions of ynones derived from glycine and (S)-alanine and some other dipolarophiles with azomethine imines, nitrile oxides, diazoacetate, and azidoacetate were studied. The dipolarophiles were obtained from α-amino acids, either by the reduction of the carboxy function with ethynylmagnesium bromide or by propiolation of the amino function. Cu-catalyzed cycloadditions of ynones to azomethine imines were regioselective and gave the expected cycloadducts as inseparable mixtures of diastereomers. In some instances, further oxidative hydrolytic ring-opening took place to afford 3,3-dimethyl-3-(1H-pyrazol-1-yl)propanoic acids. Acid-catalyzed cycloadditions of 3-butenone were also regioselective and provided mixtures of diastereomeric cycloadducts, which were separated by chromatography. In the reactions of title ynones with alkyl diazoacetates, in situ-formed benzonitrile oxides, and tert-butyl azidoacetate, all cycloadducts were obtained as single regioisomers. The structures of all novel compounds were established by nuclear magnetic resonance and X-ray diffraction.

Keywords: [3+2] cycloadditions; azomethine imines; heterocycles; pyrazolidinones; regioselectivity; stereoselectivity

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About the article

Received: 2018-01-16

Accepted: 2018-02-19

Published Online: 2018-06-08


Citation Information: Zeitschrift für Naturforschung B, 20180013, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2018-0013.

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