Cobalt-Catalyzed Asymmetric Hydrogenation of Enamides : Insights into Mechanisms and Solvent Effects
© 2022 The Authors. Published by American Chemical Society.
| Veröffentlicht in: | Organometallics. - 1998. - 41(2022), 14 vom: 25. Juli, Seite 1872-1882 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2022
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| Zugriff auf das übergeordnete Werk: | Organometallics |
| Schlagworte: | Journal Article |
| Zusammenfassung: | © 2022 The Authors. Published by American Chemical Society. The mechanistic details of the (PhBPE)Co-catalyzed asymmetric hydrogenation of enamides are investigated using computational and experimental approaches. Four mechanistic possibilities are compared: a direct Co(0)/Co(II) redox path, a metathesis pathway, a nonredox Co(II) mechanism featuring an aza-metallacycle, and a possible enamide-imine tautomerization pathway. The results indicate that the operative mechanism may depend on the type of enamide. Explicit solvent is found to be crucial for the stabilization of transition states and for a proper estimation of the enantiomeric excess. The combined results highlight the complexity of base-metal-catalyzed hydrogenations but do also provide guiding principles for a mechanistic understanding of these systems, where protic substrates can be expected to open up nonredox hydrogenation pathways |
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| Beschreibung: | Date Revised 01.09.2024 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 0276-7333 |
| DOI: | 10.1021/acs.organomet.2c00180 |