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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Bibliographic Details
Main Author: Weber, Felicia
Contributors: Hilt, Gerhard (Prof. Dr.) (Thesis advisor)
Format: Dissertation
Language:English
Published: Philipps-Universität Marburg 2018
Chemie
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Online Access:PDF Full Text
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Summary: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.
Physical Description:247 Pages
DOI:https://doi.org/10.17192/z2019.0118