Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
Lepori, Clément (Université Paris-Sud. Institut de Chimie Moléculaire et des Matériaux d'Orsay)
Gómez-Orellana Seguín, Pablo (Universitat Autònoma de Barcelona. Departament de Química)
Ouharzoune, Allissa (Université Paris-Sud. Institut de Chimie Moléculaire et des Matériaux d'Orsay)
Guillot, Régis (Université Paris-Sud. Institut de Chimie Moléculaire et des Matériaux d'Orsay)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)
Hannedouche, Jérôme (Université Paris-Sud. Institut de Chimie Moléculaire et des Matériaux d'Orsay)

Date:	2018
Abstract:	A well-defined low-coordinate β-diketiminatocobalt(II) alkyl complex is reported as an active precatalyst for the selective alkene cyclohydroamination of unprotected primary amines under mild conditions (rt-90 °C). The reaction mechanism has been investigated by deuterium-labeling, kinetics, and stoichiometric experiments and in-depth computational DFT studies. On the basis of these studies, we propose a stepwise noninsertive mechanism that features a rate-determining nucleophilic attack of the amido group of a monomeric cobalt(II) amidoalkene-aminoalkene adduct intermediate to the noncoordinated pendant alkene followed by a rapid proton transfer from the coordinated aminoalkene to the cyclized adduct.
Grants:	Agencia Estatal de Investigación CTQ2017-87889-P Ministerio de Economía y Competitividad CTQ2016-81797-REDC
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	DFT calculations ; Alkenes ; Cobalt ; Hydroamination ; Mechanistic studies ; Primary amines
Published in:	ACS catalysis, Vol. 8, Issue 5 (May 2018) , p. 4446-4451, ISSN 2155-5435

DOI: 10.1021/acscatal.8b00631

Postprint 6 p, 557.9 KB

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