Well-Defined β-Diketiminatocobalt(II) Complexes for Alkene Cyclohydroamination of Primary Amines
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 sto...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2018 |
| País: | España |
| Institución: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:279261 |
| Acceso en línea: | https://ddd.uab.cat/record/279261 https://dx.doi.org/urn:doi:10.1021/acscatal.8b00631 |
| Access Level: | acceso abierto |
| Palabra clave: | DFT calculations Alkenes Cobalt Hydroamination Mechanistic studies Primary amines |
| Sumario: | 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. |
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