Gleeson, Duangkamol

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Gleeson, Duangkamol
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duangkamol.gl@kmitl.ac.th

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    Item type:Publication,
    Computational Investigation of the Ru-Mediated Preparation of Benzothiazoles From N-Arylthioureas: Elucidation of the Reaction Mechanism and the Origin of Differing Substrate Reactivity
    (2024-10-01)
    Krawmanee, Pacharaporn
    ;
    Gleeson, M. Paul
    ;
    Gleeson, Duangkamol
    Synthesis of novel benzothiazoles via intramolecular CS bond formation reactions is increasingly being explored since they have been found in a wide range of natural products and pharmaceutical agents. Sharma et al. reported the ruthenium-catalyzed preparation of novel benzothiazole derivatives from N-arylthiourea precursors, with a range of reaction yields and selectivity being observed. We have employed a density functional theory-based computational model to investigate the reaction mechanism leading to the benzothiazole product and help uncover the origin of the differing experimental yields and substrate specificities. We proposed a modified mechanistic scheme where the rate-determining step to be the synchronized breaking of the peroxide bond of the oxidizing agent with the concomitant proton-coupled electron transfer from the haloarene urea and a Ru-bound water molecule, not electrophilic RuC bond activation. Evidence for this being the rate-determining step is (a) the barrier is consistent with a lack of kinetic isotope effects associated with the ortho-H atom and (b) the computed rate-determining barriers for 10 N-arylthiourea substrates show good correlation with the observed yield.