title: Well-defined four-coordinate iron(II) complexes for intramolecular hydroamination of primary aliphatic alkenylamines.
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(NHCH2 CPh2 CH2 CH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.
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR CNRS 8182, Univ Paris-Sud, Orsay, 91405 (France).
authors.forename: Elise
authors.initials: E
authors.lastname: Bernoud
authors.forename: Pascal
authors.initials: P
authors.lastname: Oulié
authors.forename: Régis
authors.initials: R
authors.lastname: Guillot
authors.forename: Mohamed
authors.initials: M
authors.lastname: Mellah
authors.forename: Jérôme
authors.initials: J
authors.lastname: Hannedouche
keywords: alkenes; amines; homogeneous catalysis; hydroamination; iron