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Well‐Defined Four‐Coordinate Iron(II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines
Author(s) -
Bernoud Elise,
Oulié Pascal,
Guillot Régis,
Mellah Mohamed,
Hannedouche Jérôme
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201402089
Subject(s) - hydroamination , aminolysis , chemistry , alkene , intramolecular force , catalysis , primary (astronomy) , reactivity (psychology) , dimer , alkyl , alkyne , medicinal chemistry , stereochemistry , organic chemistry , medicine , physics , alternative medicine , pathology , astronomy
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(NHCH 2 CPh 2 CH 2 CHCH 2 )] 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.