A challenging redox neutral Cp*Co(III)-catalysed alkylation of acetanilides with 3-buten-2-one: synthesis and key insights into the mechanism through DFT calculations

KENNY, Andrew, PISARELLO, Alba, BIRD, Arron, CHIRILA, Paula G, HAMILTON, Alexander and WHITEOAK, Christopher (2018). A challenging redox neutral Cp*Co(III)-catalysed alkylation of acetanilides with 3-buten-2-one: synthesis and key insights into the mechanism through DFT calculations. Beilstein journal of organic chemistry, 14, 2366-2374.

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Official URL: https://www.beilstein-journals.org/bjoc/articles/1...
Link to published version:: https://doi.org/10.3762/bjoc.14.212
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    Abstract

    Traditional, established palladium cross-coupling procedures are widely applied in complex molecule synthesis; however, there is a significant disadvantage in the requirement for pre-functionalised substrates (commonly halides/triflates). Direct C–H activation protocols provide the opportunity for a novel approach to synthesis, although this field is still in its relative infancy and often transferability between substrate classes remains unresolved and limitations not fully understood. This study focuses on the translation of an established Cp*Co(III)-catalysed alkylation of benzamides to related acetanilides using 3-buten-2-one as coupling partner. The developed procedure provides a wide substrate scope in terms of substituted acetanilides, although the optimised conditions were found to be more forcing than those for the corresponding benzamide substrates. Interestingly, density functional theory (DFT) studies reveal that the major impediment in the mechanism is not the C–H activation step, but instead and unexpectedly, effective competition with more stable compounds (resting states) not involved in the catalytic cycle.

    Item Type: Article
    Research Institute, Centre or Group - Does NOT include content added after October 2018: Biomolecular Sciences Research Centre
    Departments - Does NOT include content added after October 2018: Health and Well-being > Department of Bioscience
    Identification Number: https://doi.org/10.3762/bjoc.14.212
    Page Range: 2366-2374
    Depositing User: Christopher Whiteoak
    Date Deposited: 13 Sep 2018 10:53
    Last Modified: 18 Jun 2020 17:08
    URI: http://shura.shu.ac.uk/id/eprint/22466

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