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Scope, Application and Mechanistic Details of the Nickel-Catalyzed Z-Selective Isomerization of Terminal Olefins
In this dissertation, the mechanism of the nickel-catalyzed Z-selective isomerization of terminal alkenes with the additive diphenylphosphine could be successfully clarified. The nickel-catalyzed Z-selective isomerization of terminal alkenes was successfully applied as key step in the synthesis of t...
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| Формат: | Dissertation |
| Мова: | Англійська |
| Опубліковано: |
Philipps-Universität Marburg
2018
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| Онлайн доступ: | PDF-повний текст |
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| Резюме: | In this dissertation, the mechanism of the nickel-catalyzed Z-selective isomerization of terminal alkenes with the additive diphenylphosphine could be successfully clarified. The nickel-catalyzed Z-selective isomerization of terminal alkenes was successfully applied as key step in the synthesis of the pheromone of the beet armyworm spodoptera exigua, (9Z,12Z)-tetradeca-9,12-dien-1-yl acetate (165). For the final isomerization step, Ni(dppe)Cl2 emerged as the pre-catalyst of choice. Regarding the diversification of the substrate scope, secondary and tertiary N-allyl amides and carbamates were well-tolerated. The feature of the method was a substrate-specific isomerization. Secondary amides (and carbamates) predominantly formed the Z-configured enamide (and enecarbamate, respectively), whereas tertiary amides and oxazolidinones gave the E-configured product. The final challenge of the catalyst system was the tolerance towards functional groups, which
were not located in the substrate itself, but additional reactants. According to this, a diastereoselective isomerization/allylboration sequence was realized and up to 96% syn-selectivity could be achieved. |
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| Фізичний опис: | 247 Seiten |
| DOI: | 10.17192/z2019.0118 |