Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols
journal contributionposted on 06.03.2020, 15:46 by Sara Sabater, Maximilian Menche, Tamal Ghosh, Saskia Krieg, Katharina S. L. Rück, Rocco Paciello, Ansgar Schäfer, Peter Comba, A. Stephen K. Hashmi, Thomas Schaub
The carbonylation of alcohols represents a straightforward and atom-efficient methodology for the preparation of carboxylic acids. It is desirable to perform these reactions under precious metal-free and low-pressure conditions, with regioselectivity control. In this work, we present a detailed mechanistic study of a catalytic system based on NiI2, which can carbonylate benzylic alcohols in a highly regioselective manner to the corresponding branched carboxylic acids, core motifs for nonsteroidal drugs. The combination of catalytic amounts of nickel and iodide is crucial for efficient catalytic and regioselective conversion. Quantum-chemical computations were used to evaluate the underlying mechanistic processes. They revealed that a combination of two mechanisms is responsible for the observed reactivity and that the oxidative addition of alkyl halides to the Ni(0) species follows a radical oxidation pathway via two one-electron steps.
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NiCarbonylationatom-efficientmotifInvestigationmannercomputationQuantum-chemicalcarboxylic acidsspeciescarbonylate benzylic alcoholsregioselectivitycarbonylationregioselectivehalidesnonsteroidalMechanisticmethodologyiodidepathwaycorecombinationmechanismoxidationNickel-Catalyzedconversionmetal-freeoxidativealkylpreparationlow-pressureone-electronNiIreactivity