Well- Defined Four- Coordinate Iron( II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines**

被引：64

作者：

Bernoud, Elise ^{[1
]}

Oulie, Pascal ^{[1
]}

Guillot, Regis ^{[1
]}

Mellah, Mohamed ^{[1
]}

Hannedouche, Jerome ^{[1
]}

机构：

[1] Univ Paris 11, ICMMO, CNRS, UMR 8182, F-91405 Orsay, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 19期

关键词：

alkenes; amines; homogeneous catalysis; hydroamination; iron; UNACTIVATED ALKENES; ENANTIOSELECTIVE HYDROAMINATION; INTERMOLECULAR HYDROAMINATION; CATALYZED HYDROAMINATION; C-N; ALKYL; 3-COORDINATE; RHODIUM; NITROGEN; CYCLIZATION;

D O I：

10.1002/anie.201402089

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 -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 degrees C). Both empirical kinetic analyses and the reactivity of an isolated iron(II) amidoalkene dimer, [LFe(NHCH2CPh2CH2CHCH2)](2) favor a stepwise sigma-insertive mechanism that entails migratory insertion of the pendant alkene into an iron-amido bond associated with a rate-determining aminolysis step.

引用

页码：4930 / 4934

页数：5