Electro-mediated photoredox catalysis for selective C(sp3)–O cleavages of phosphinated alcohols to carbanions

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Tian, Xianhai and Karl, Tobias A. and Reiter, Sebastian and Yakubov, Shahboz and de Vivie-Riedle, Regina and König, Burkhard and Barham, Joshua P. (2021) Electro-mediated photoredox catalysis for selective C(sp3)–O cleavages of phosphinated alcohols to carbanions. Angewandte Chemie - International Edition, 60 (38). pp. 20817-20825. ISSN 1521-3773 (https://doi.org/10.1002/anie.202105895)

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Abstract

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3)−O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp3)−O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.

ORCID iDs

Tian, Xianhai, Karl, Tobias A., Reiter, Sebastian, Yakubov, Shahboz, de Vivie-Riedle, Regina, König, Burkhard and Barham, Joshua P. ORCID logoORCID: https://orcid.org/0000-0003-1675-9399;
  • Item type:Article
    ID code:92119
    Dates:
    Date
    Event
    13 September 2021
    Published
    24 June 2021
    Published Online
    21 June 2021
    Accepted
    Notes:Publisher Copyright: © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:20 Feb 2025 12:10
    Last modified:20 Feb 2025 12:10
    URI:https://strathprints.strath.ac.uk/id/eprint/92119
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