Cyclische Alpha- und Ortho-Lithio-S-Phenyl-Sulfoximine : Synthese, Funktionalisierung und Umlagerung

The target of this thesis was the synthesis of different substituted cyclic sulfoximines suitable for the use as ligands in the asymmetric 1,4-addition. This aim was tried to achieve through synthesis of different substituted cyclic sulfoximines for the use as chiral nontransferable ligands in the stoichometric conjugate addition. Another topic was the synthesis of sulfoximines which could work as ligands in the catalytic conjugate addition. The ortho directed lithiation used for the ortho-alkylation of the cyclic sulfoximines worked with good yields and selectivities. Unfortunately the further functionalisation in ortho-position with different donor atoms for the use as chiral ligands failed. The reactivity of cyclic sulfoximines was investigated in different metallation and deuteration experiments. An interesting rearrangement occured for the dimethyl substituted cyclic sulfoximines. By ortho-lithiation of this sulfoximines and warming up to room temperature the sulfoximines rearranged to 2-aminothiobenzene-derivatives. This rearrangement reaction was further investigated by NMR-experiments and it was possible to determine the configuration at the sulfur atom after the rearrangement by an X-ray analysis. The reaction proceeded under inversion of the configuration. The enantiomeric pure rearrangement products belong to a pharmaceutical interesting group of compounds. The stoichometic conjugate addition with cyclic sulfoximines as chiral non transferable ligands with cuprates was carried out with exellent yields but moderate enantioselectivities. In the catalytic enantioselective conjugte addition good yields but only moderate enantioselctivities were achieved with the neutral sulfoximines.

Grantor dc:publisher

Publikationsserver der RWTH Aachen University

Year dc:date

2002

Author dc:creator

• Wessels, Michael

Contributors dc:contributor

• Gais, Hans-Joachim

• info:eu-repo/classification/ddc/540
• Chemie

Statement dc:rights

• info:eu-repo/semantics/openAccess

Language dc:language

ger

Identifier

https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-118978%22

OAI identifier oai:identifier

oai:publications.rwth-aachen.de:56902