Chirale Sulfonimidamide und Sulfoximine : Synthese, Strukturuntersuchungen und Anwendungen

摘要

This thesis describes the synthesis and structure determination of chiral sulfur-containing compounds, their use in asymmetric catalysis and the determination of the basicity of a bissulfoximine. In the first part the preparation of enantio- and diastereomerically pure sulfonimidamides bearing either an oxazolidinyl or a cyclohexylamino moiety is described, as well as the synthesis of enantiopure oxazolinyl-derivatized thioureas and one enantiopure oxazolinyl-functionalized guanidine. The structures of the oxazolidinyl-functionalized sulfonimidamides and the oxazolinyl-derivatized thioureas were examined by NMR- and X-ray methods. Furthermore, the first example of an asymmetric metal catalysis using sulfonimidamides as ligands is presented: the cyclohexylamine derived sulfonimidamides were applied in the Cu-catalyzed asymmetric Henry reaction between aromatic aldehydes and nitromethane giving products with enantiomeric excesses up to 95% ee. In the second part of this thesis the basicity of a C2-symmetric naphthaline based bissulfoximine was studied, since this compound shows structural similarities to so-called proton sponges. Protonation experiments towards the determination of the basicity were carried out and the kinetic activity of the bissulfoximine was determined in a proton self-exchange reaction. A discussion of the structures of the free base and the protonated species is done using the data obtained from X-ray analysis. Finally, quantum chemical calculations for the determination of the proton affinity of the bissulfoximine are described.