Well‐Defined Four‐Coordinate Iron(II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines |
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Authors: | Dr Elise Bernoud Dr Pascal Oulié Dr Régis Guillot Dr Mohamed Mellah Dr Jérôme Hannedouche |
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Institution: | Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR CNRS 8182, Univ Paris‐Sud, Orsay, 91405 (France) |
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Abstract: | Despite the growing interest in iron catalysis and hydroamination reactions, iron‐catalyzed hydroamination of unprotected primary aliphatic amines and unactivated alkenes has not been reported to date. Herein, a novel well‐defined four‐coordinate β‐diketiminatoiron(II) alkyl complex is shown to be an excellent precatalyst for the highly selective cyclohydroamination of primary aliphatic alkenylamines at mild temperatures (70–90 °C). Both empirical kinetic analyses and the reactivity of an isolated iron(II) amidoalkene dimer, LFe(NHCH2CPh2CH2CH?CH2)]2 favor a stepwise σ‐insertive mechanism that entails migratory insertion of the pendant alkene into an iron–amido bond associated with a rate‐determining aminolysis step. |
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Keywords: | alkenes amines homogeneous catalysis hydroamination iron |
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