Boosting the nucleophilicity of the diphenylphosphide anion with crown ether supported heavy alkali metals to facilitate highly efficient catalytic alkene isomerization

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Krämer, Felix and Horsley Downie, Thomas M. and Mulvey, Robert E. (2026) Boosting the nucleophilicity of the diphenylphosphide anion with crown ether supported heavy alkali metals to facilitate highly efficient catalytic alkene isomerization. Angewandte Chemie International Edition. e23460. ISSN 1521-3773 (https://doi.org/10.1002/anie.202523460)

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Abstract

Caesium and rubidium have long experienced an interest drought in organoelement chemistry in comparison to the vast ocean of applications accomplished mainly by lithium and to a lesser extent, by sodium and potassium in this field. Here, we report a breakthrough study in catalytic alkene isomerisation using crown ether-supported alkali metal phosphides in which the activity increases sequentially and significantly as Group One is descended with Cs(18-crown-6)PPh2 performing best even at 1 mol% loadings with high turnover frequencies (TOFs) and good functional group tolerance. Elevating its profile further, Cs(18-crown-6)PPh2 is also successful in a stepwise double catalysis on combining alkene isomerisation with its newly established hydrophosphination (HP) capacity to access challenging to make Markovnikov products. This remote functionalisation approach was also applied to alkynes with terminal alkynes preferentially producing allenes over internal alkynes in one-pot reactions and then under HP, generating highly functionalised vinyl phosphines. Kinetic studies and DFT calculations have also been performed to shed light on mechanistic aspects of the Cs-mediated isomerisation of model alkene allylbenzene.

ORCID iDs

Krämer, Felix, Horsley Downie, Thomas M. ORCID logoORCID: https://orcid.org/0000-0001-5027-450X and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:95090
    Dates:
    Date
    Event
    20 January 2026
    Published
    20 January 2026
    Published Online
    16 December 2025
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:18 Dec 2025 16:43
    Last modified:02 Feb 2026 08:50
    URI:https://strathprints.strath.ac.uk/id/eprint/95090
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