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Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
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Styrene Aziridination by Iron(IV) Nitrides.
Salvador B Muñoz1, Wei-Tsung Lee1, Diane A Dickie2
1Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, IN 47403 (USA).
Angewandte Chemie (International Ed. in English)
|July 17, 2015
Summary
Iron nitride complexes facilitate styrene aziridination, forming aziridino complexes. This reaction enables cross-metathesis and N-functionalized aziridine synthesis, demonstrating a closed synthetic cycle for nitride complex chemistry.
Area of Science:
- Organometallic Chemistry
- Synthetic Chemistry
- Nitrogen Chemistry
Background:
- Iron nitride complexes are reactive species with potential in organic synthesis.
- Aziridination of alkenes is a key transformation for synthesizing nitrogen-containing heterocycles.
Purpose of the Study:
- To investigate the thermolysis of an iron(IV) nitride complex with styrene.
- To explore the utility of the resulting iron(II) aziridino complex as a nitride synthon.
- To establish a synthetic cycle for styrene aziridination.
Main Methods:
- Thermolysis of [PhB(tBuIm)3Fe≡N] with various styrenes.
- Characterization of iron complexes and aziridino products.
- Reaction of the aziridino complex with Me3SiCl to generate N-functionalized aziridines.
Main Results:
- Formation of high-spin iron(II) aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)] from iron(IV) nitride and styrene.
- Aziridination occurs with electron-rich and electron-poor styrenes, but is hindered by bulky styrenes.
- The aziridino complex mediates aziridine cross-metathesis and reacts with Me3SiCl to yield N-functionalized aziridines, closing a synthetic cycle.
Conclusions:
- Iron nitride complexes are effective reagents for styrene aziridination.
- The aziridino complex serves as a versatile nitride synthon for further transformations.
- A complete synthetic cycle for styrene aziridination using a nitride complex has been established.
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