Synthesis of functionalized pyrazole derivatives by regioselective [3+2] cycloadditions of N-Boc-α-amino acid-derived ynones
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Eva Pušavec Kirar
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.
Acknowledgment
We are grateful to Slovenian Research Agency, program code P1-0179, for financial support. We also thank the EN-FIST Centre of Excellence (Ljubljana, Slovenia) for use of the SuperNova dual-source diffractometer and Alpha Platinum FTIR spectrometer.
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©2018 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- In this Issue
- Preface
- The role of iminium salts, imines and related compounds in chemistry
- Original Articles
- A simple route to 2-aryl-substituted naphtho[2,1-e][1,2,4]triazinium and naphtho[2,1-e][1,2,3,4]tetrazinium salts from 1-arylazo-substituted 2-naphthylamines
- Orthoamide und Iminiumsalze, XCII. Synthese und Reaktionen von Orthoamiden aus ethinylierten Terpenderivatena
- Orthoamide und Iminiumsalze, XCIII. Darstellung und Umsetzungen eines vinylogen Orthoamid-Derivats der Kohlensäure mit CH2-aciden Verbindungena
- Synthesis of functionalized pyrazole derivatives by regioselective [3+2] cycloadditions of N-Boc-α-amino acid-derived ynones
- Chemistry and spectroscopy of cross-conjugated and pseudo-cross-conjugated quinolinium-ethynyl-benzoate mesomeric betaines
- Integrating the fluorene substructure into azaacenes: syntheses of novel fluorophores
- Thermal metal-free [2+2] cycloaddition of acetylenedicarboxylates to polysubstituted butadienes
- Protic ionic liquids as catalysts for a three-component coupling/hydroarylation/dehydrogenation tandem reaction
- Review
- Iminiumsalz-Strukturen bei der durch Pyridoxalphosphat (Vitamin B6) katalysierten Bildung von Aromastoffen und Fehlaromen im Wein
Artikel in diesem Heft
- Frontmatter
- In this Issue
- Preface
- The role of iminium salts, imines and related compounds in chemistry
- Original Articles
- A simple route to 2-aryl-substituted naphtho[2,1-e][1,2,4]triazinium and naphtho[2,1-e][1,2,3,4]tetrazinium salts from 1-arylazo-substituted 2-naphthylamines
- Orthoamide und Iminiumsalze, XCII. Synthese und Reaktionen von Orthoamiden aus ethinylierten Terpenderivatena
- Orthoamide und Iminiumsalze, XCIII. Darstellung und Umsetzungen eines vinylogen Orthoamid-Derivats der Kohlensäure mit CH2-aciden Verbindungena
- Synthesis of functionalized pyrazole derivatives by regioselective [3+2] cycloadditions of N-Boc-α-amino acid-derived ynones
- Chemistry and spectroscopy of cross-conjugated and pseudo-cross-conjugated quinolinium-ethynyl-benzoate mesomeric betaines
- Integrating the fluorene substructure into azaacenes: syntheses of novel fluorophores
- Thermal metal-free [2+2] cycloaddition of acetylenedicarboxylates to polysubstituted butadienes
- Protic ionic liquids as catalysts for a three-component coupling/hydroarylation/dehydrogenation tandem reaction
- Review
- Iminiumsalz-Strukturen bei der durch Pyridoxalphosphat (Vitamin B6) katalysierten Bildung von Aromastoffen und Fehlaromen im Wein
