Styrene Aziridination by Iron(IV) Nitrides

• Published in: Angewandte Chemie International Edition 2015-09, Vol.54 (36), p.10600-10603
• Main Authors: Muñoz III, Salvador B., Lee, Wei-Tsung, Dickie, Diane A., Scepaniak, Jeremiah J., Subedi, Deepak, Pink, Maren, Johnson, Michael D., Smith, Jeremy M.
• Format: Article
• Language: English
• Subjects: alkenes; Aziridines - chemistry; Electron spin; Formations; Iron; Iron Compounds - chemistry; Metathesis; Nitrides; Nitrogen Compounds - chemistry; Styrene; Styrene - chemistry; Styrenes; Temperature effects
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201503773

Thermolysis of the iron(IV) nitride complex [PhB(tBuIm)3FeN] with styrene leads to formation of the high‐spin iron(II) aziridino complex [PhB(tBuIm)3Fe‐N(CH2CHPh)]. Similar aziridination occurs with both electron‐rich and electron‐poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex [PhB(tBuIm)3Fe‐N(CH2CHPh)] acts as a nitride synthon, reacting with electron‐poor styrenes to generate their corresponding aziridino complexes, that is, aziridine cross‐metathesis. Reaction of [PhB(tBuIm)3Fe‐N(CH2CHPh)] with Me3SiCl releases the N‐functionalized aziridine Me3SiN(CH2CHPh) while simultaneously generating [PhB(tBuIm)3FeCl]. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex [PhB(MesIm)3FeN] reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products. New access to versatile synthons: Iron(IV) nitride complexes react with a range of styrenes to form the corresponding high‐spin iron(II) aziridino complexes. The reversibility of the aziridination reaction allows for aziridine cross‐metathesis reactions. A synthetic cycle for the formation of N‐silylated aziridines has been established.