Asymmetrische Synthese von allylischen Alkoholen mittels Palladium-katalysierter asymmetrischer Transformation von allylischen Carbonaten und Synthese neuer Sulfoximin-Phosphane

This thesis deals with two areas of study. The first part focuses on the asymmetric synthesis of synthetically interesting allylic alcohols by Palladium-catalyzed allylic substitution. For this substitution reaction the hydrogen carbonate ions are used as nucleophil and racemic allylic carbonates or acetates as racemic substrates. This reaction can also be called asymmetrical transformation (AT) or dynamic-kinetic asymmetric transformation (DYKAT). The investigations carried out to the AT and DYKAT of different natural product building blocks show that the used catalyst complexes have some weaknesses with regard to demanding substrates. The catalyst complexes of the bisphoshpane ligands are either sterically too demanding or the DYKAT leads to unexpected products. However, it is unlikely that this is caused by the method used, but it is more likely to be a problem of the used ligands. The possibility to apply this method to the synthesis of chiral allylic alcohols on bigger substrate amounts was shown by the synthesis of the synthetically valuable allylic alcohol, Cyclopent-2-en-1-ol, in the gramme area. The second part of this thesis is devoted to the development of new sulfoximine ligands and methods of their synthesis. On this occasion, interesting new classes of sulfoximines, alpha-(N-sulfoximido) phosphines, phosphine oxides and phosphonates, were synthesized from N-vinyl sulfoximines. These new sulfoximines could possibly serve as ligands or as an analogue to the bioactive alpha-aminophosphonic acids. Further investigations of the N-vinyl sulfoximines showed an enamine-like reactivity in acid-catalyzed hydrolysis, hydroboration, hydrophosphination and hydrophosphorylation (Pudovik-Reaction). Furthermore, the hydroboration / oxidation of N-vinylic sulfoximines opens up the possibility to receive other potential sulfoximine ligands via N-(beta-hydroxy) sulfoximines.

Grantor dc:publisher

Publikationsserver der RWTH Aachen University

Year dc:date

2008

Author dc:creator

• Hetzer, Ralf Helmut

Contributors dc:contributor

• Gais, Hans-Joachim

• info:eu-repo/classification/ddc/540
• Allyl-Stellung
• Allylmetallverbindungen
• Palladiumkomplexe
• Palladium
• Stereoselektive Synthese
• Asymmetrische Synthese
• Homogene Katalyse
• Katalyse
• Chemie
• Sulfoximin
• DYKAT
• asymmetrische Transformation
• Phosphane
• Phosphonate
• Pudovik
• allylische Substitution
• Allylalkohol
• Ligand
• sulfoximine
• asymmetric transformation
• phosphine
• allylic substitution
• allylic alcohol, ligand

Statement dc:rights

• info:eu-repo/semantics/openAccess

Language dc:language

ger

Identifier

https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-112648%22

OAI record oai:identifier

https://publications.rwth-aachen.de/oai2d?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai%3Apublications.rwth-aachen.de%3A50090