Synthese und Reaktivität fluorierter Allylalkohole

Im Rahmen dieser Arbeit wurden aus kommerziell erhältlichen Carbonsäuren in einer zweistufigen Synthese verschiedene Inone hergestellt. Diese konnten durch eine Hydrofluorierung in β-Fluorenone überführt werden. Eine anschließende asymmetrische Reduktion ermöglichte den Zugang von skalemischen 3 Flu...

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Bibliographic Details
Main Author: Zygalski, Lukas
Contributors: Koert, Ulrich (Prof. Dr.) (Thesis advisor)
Format: Doctoral Thesis
Published: Philipps-Universität Marburg 2020
Online Access:PDF Full Text
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In this thesis, different ynones were generated in a two step synthesis coming from commercial available carboxylic acids. The ynones were hydrofluorinated by the use of AgF to obtain the corresponding β-fluoroenones. An asymmetric reduction led to scalemic 3 fluoroallylic alcohols. The 3 fluoroallylic alcohols are versatile building blocks and can be used for further functionalization. Herein an epoxidation of racemic 3 fluoroallylic alcohol is reported. The desired epoxid was isolated in very good yield and good dr. Furthermore a cyclopropanation of racemic 3 fluoroallylic alcohol led to good yield and excellent dr. An OVERMAN-rearrangement of the corresponding trichloroacetimidate was not succesfull. The 3 fluoroallylic alcohols could also be converted into the trifluoroacetates, which then could be used for a rhodium catalyzed allylic substitution to introduce a nitrile group. The nitriles could be observed in good yield, very good Z/E-selectivity and perfect regioselectivity. Mechanistic experiments showed that the perfect regioselectivity is owned by the influence of the fluorine. The use of scalemic trifluoracetates led to scalemic nitriles, however a stereoerosion of approximately 10% was observed. The nitrile function was successfully converted into the corresponding carboxylic acid in a two step synthesis under mild reaction conditions.