These authors contributed equally to this work.
Well-Defined Four-Coordinate Iron(II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines†
Article first published online: 1 APR 2014
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 53, Issue 19, pages 4930–4934, May 5, 2014
How to Cite
Bernoud, E., Oulié, P., Guillot, R., Mellah, M. and Hannedouche, J. (2014), Well-Defined Four-Coordinate Iron(II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines. Angew. Chem. Int. Ed., 53: 4930–4934. doi: 10.1002/anie.201402089
We thank ANR JCJC DHAMFER, Univ Paris Sud and CNRS for financial support.
- Issue published online: 2 MAY 2014
- Article first published online: 1 APR 2014
- Manuscript Received: 5 FEB 2014
- ANR JCJC DHAMFER
- Univ Paris Sud
- homogeneous catalysis;
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(NHCH2CPh2CH2CHCH2)]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.