Revisiting nickel-catalyzed carbonylations: (unexpected) observation of substrate-dependent mechanistic differences
The (hydroxy)carbonylation of tertiary aliphatic alcohols and their corresponding olefins with a Ni-based catalyst system is investigated. This study builds on a previous mechanistic investigation into the Ni-catalyzed carbonylation of alcohols. The findings differed from what could be explained wit...
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| Main Authors: | , , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
5 May 2022
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| In: |
Organometallics
Year: 2022, Volume: 41, Issue: 10, Pages: 1184-1196 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/acs.organomet.2c00090 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.organomet.2c00090
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| Author Notes: | Niels Lichtenberger, Maximilian Menche, Katharina S.L. Rück, Rocco Paciello, Ansgar Schäfer, Peter Comba, A. Stephen K. Hashmi, and Thomas Schaub |
| Summary: | The (hydroxy)carbonylation of tertiary aliphatic alcohols and their corresponding olefins with a Ni-based catalyst system is investigated. This study builds on a previous mechanistic investigation into the Ni-catalyzed carbonylation of alcohols. The findings differed from what could be explained with the previously reported mechanisms, prompting this in-depth mechanistic study. Combined experimental and quantum chemical efforts are crucial for the rationalization of the observed reactivities and ultimately help reveal another isobutene-based catalytic pathway, accessible with these substrates. This study further expands the knowledge about Ni-catalyzed carbonylation reactions, which have been known for more than 70 years but were scarcely studied in detail from a mechanistic point of view. |
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| Item Description: | Gesehen am 06.07.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/acs.organomet.2c00090 |