Abstract
Copyright © 2018 American Chemical Society. 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.
Original language | English |
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Pages (from-to) | 4446-4451 |
Journal | ACS Catalysis |
Volume | 8 |
Issue number | 5 |
DOIs | |
Publication status | Published - 4 May 2018 |
Keywords
- DFT calculations
- alkenes
- cobalt
- hydroamination
- mechanistic studies
- primary amines