Mechanism, Reactivity, and Selectivity of Nickel-Catalyzed [4 + 4 + 2] Cycloadditions of Dienes and Alkynes
| العنوان: | Mechanism, Reactivity, and Selectivity of Nickel-Catalyzed [4 + 4 + 2] Cycloadditions of Dienes and Alkynes |
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| المؤلفون: | Dane Holte, Daniel C. G. Götz, Phil S. Baran, Xin Hong, Kendall N. Houk |
| المصدر: | The Journal of Organic Chemistry The Journal of organic chemistry, vol 79, iss 24 |
| بيانات النشر: | American Chemical Society (ACS), 2014. |
| سنة النشر: | 2014 |
| مصطلحات موضوعية: | Stereochemistry, chemistry.chemical_element, Alkyne, Alkenes, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Article, Catalysis, Medicinal and Biomolecular Chemistry, Isomerism, Nickel, Reactivity (chemistry), chemistry.chemical_classification, Exergonic reaction, Cycloaddition Reaction, Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, Cycloaddition, 0104 chemical sciences, Alkynes, Quantum Theory, Density functional theory, Selectivity, Oxidation-Reduction |
| الوصف: | Density functional theory (DFT) calculations with B3LYP and M06 functionals elucidated the reactivities of alkynes and Z/E selectivity of cyclodecatriene products in the Ni-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes. The Ni-mediated oxidative cyclization of butadienes determines the Z/E selectivity. Only the oxidative cyclization of one s-cis to one s-trans butadiene is facile and exergonic, leading to the observed 1Z,4Z,8E-cyclodecatriene product. The same step with two s-cis or s-trans butadienes is either kinetically or thermodynamically unfavorable, and the 1Z,4E,8E- and 1Z,4Z,8Z-cyclodecatriene isomers are not observed in experiments. In addition, the competition between the desired cooligomerization and [2 + 2 + 2] cycloadditions of alkynes depends on the coordination of alkynes. With either electron-deficient alkynes or alkynes with free hydroxyl groups, the coordination of alkynes is stronger than that of dienes, and alkyne trimerization prevails. With alkyl-substituted alkynes, the generation of alkyne-coordinated nickel complex is much less favorable, and the [4 + 4 + 2] cycloaddition occurs. |
| وصف الملف: | application/pdf |
| تدمد: | 1520-6904 0022-3263 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::9a43d764e2d6a624f71161f6f8af168e https://doi.org/10.1021/jo502219d |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....9a43d764e2d6a624f71161f6f8af168e |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15206904 00223263 |
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