Computational Exploration of the Mechanism of Critical Steps in the Biomimetic Synthesis of Preuisolactone A, and Discovery of New Ambimodal (5 + 2)/(4 + 2) Cycloadditions
| العنوان: | Computational Exploration of the Mechanism of Critical Steps in the Biomimetic Synthesis of Preuisolactone A, and Discovery of New Ambimodal (5 + 2)/(4 + 2) Cycloadditions |
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| المؤلفون: | Xiao-Song Xue, Kendall N. Houk, Alexander J. E. Novak, Shuming Chen, Cooper S. Jamieson, Dirk Trauner, Hong Zhang |
| المصدر: | Journal of the American Chemical Society. 143:6601-6608 |
| بيانات النشر: | American Chemical Society (ACS), 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | Cycloaddition Reaction, Chemistry, Quinones, General Chemistry, Ring (chemistry), Biochemistry, Catalysis, Cycloaddition, Hydroquinones, Adduct, Benzilic acid rearrangement, Bicarbonates, Lactones, Molecular dynamics, Colloid and Surface Chemistry, Deprotonation, Biomimetics, Computational chemistry, Biomimetic synthesis, Density functional theory, Sesquiterpenes |
| الوصف: | Computational studies with ωB97X-D density functional theory of the mechanisms of the steps in Trauner's biomimetic synthesis of preuisolactone A have elaborated and refined mechanisms of several unique processes. An ambimodal transition state has been identified for the cycloaddition between an o-quinone and a hydroxy-o-quinone; this leads to both (5 + 2) (with H shift) and (4 + 2) cycloaddition products, which can in principle interconvert via α-ketol rearrangements. The origins of periselectivity of this ambimodal cycloaddition have been investigated computationally with molecular dynamics simulations and tested further by an experimental study. In the presence of bicarbonate ions, the deprotonated hydroxy-o-quinone leads to only the (5 + 2) cycloaddition adduct. A new mechanism for a benzilic acid rearrangement resulting in ring contraction is proposed. |
| تدمد: | 1520-5126 0002-7863 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::5b8a774e21f1535c091c1c746fd7f49a https://doi.org/10.1021/jacs.1c01856 |
| حقوق: | CLOSED |
| رقم الأكسشن: | edsair.doi.dedup.....5b8a774e21f1535c091c1c746fd7f49a |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15205126 00027863 |
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