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Keywords:

  • alkenes;
  • amines;
  • homogeneous catalysis;
  • hydroamination;
  • iron

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[DOUBLE BOND]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.