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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Hauptverfasser: Lichtenberger, Niels (VerfasserIn) , Menche, Maximilian (VerfasserIn) , Rück, Katharina (VerfasserIn) , Paciello, Rocco (VerfasserIn) , Schäfer, Ansgar (VerfasserIn) , Comba, Peter (VerfasserIn) , Hashmi, A. Stephen K. (VerfasserIn) , Schaub, Thomas (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 5 May 2022
In: Organometallics
Year: 2022, Jahrgang: 41, Heft: 10, Pages: 1184-1196
ISSN:1520-6041
DOI:10.1021/acs.organomet.2c00090
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.organomet.2c00090
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Verfasserangaben:Niels Lichtenberger, Maximilian Menche, Katharina S.L. Rück, Rocco Paciello, Ansgar Schäfer, Peter Comba, A. Stephen K. Hashmi, and Thomas Schaub

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520 |a 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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