Item type:Thesis, Open Access

Scope, Application and Mechanistic Details of the Nickel-Catalyzed Z-Selective Isomerization of Terminal Olefins

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2019-11-05

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Philipps-Universität Marburg
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Abstract

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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Dates
Created: 2018Issued: 2019-11-05Updated: 2019-11-05
DOI
https://doi.org/10.17192/z2019.0118
Faculty
Fachbereich Chemie
Publisher
Philipps-Universität Marburg
Language
eng
Data types
DoctoralThesis
Keywords
Nickel-CatalysisOlefin IsomerisierungNickel-KatalyseZ-SelektivitätZ-SelectivityOlefin Isomerization
DFG-subjects
MechanismusNickel-KatalyseIsomerisierungStereoselektivität
DDC-Numbers
540
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https://rightsstatements.org/vocab/InC-NC/1.0/
URI
https://open.uni-marburg.de/handle/10.17192/z2019.0118
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Weber, Felicia: Scope, Application and Mechanistic Details of the Nickel-Catalyzed Z-Selective Isomerization of Terminal Olefins. : Philipps-Universität Marburg 2019-11-05. DOI: https://doi.org/10.17192/z2019.0118.

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