Braunschweig, Techn. Universiẗat, Diss., 2001.

München, Univ., Diss., 2004. / Computerdatei im Fernzugriff.

Verdazyl radicals are a unique class of stable radicals that have found uses as reporter molecules in biological systems, substrates for molecular-based magnets and mediators in living radical polymerizations. Over the past few years, our laboratory has pioneered the use of verdazyl radicals as substrates in 1,3-dipolar cycloaddition reactions to provide unique small molecule five-membered ring systems containing structural features commonly found in therapeutic agents. As an extension to this work we became interested in seeing whether this chemistry could be applied to the synthesis of macrocyclic scaffolds, in particular cyclophanes. Cyclophanes have been attractive synthetic targets for organic chemists because of their unique structural properties, conformational behaviours and molecular recognition capabilities. Presented in this thesis is the successful demonstration of the extension of the verdazyl chemistry to novel [n]-paracyclophanes. The structural features and conformational biases of these molecules as evidenced by 1H-NMR and X-ray crystallography are highlighted along with molecular recognition studies.

Verdazyl radicals are a unique class of stable radicals that have found uses as reporter molecules in biological systems, substrates for molecular-based magnets and mediators in living radical polymerizations. Over the past few years, our laboratory has pioneered the use of verdazyl radicals as substrates in 1,3-dipolar cycloaddition reactions to provide unique small molecule five-membered ring systems containing structural features commonly found in therapeutic agents. As an extension to this work we became interested in seeing whether this chemistry could be applied to the synthesis of macrocyclic scaffolds, in particular cyclophanes. Cyclophanes have been attractive synthetic targets for organic chemists because of their unique structural properties, conformational behaviours and molecular recognition capabilities. Presented in this thesis is the successful demonstration of the extension of the verdazyl chemistry to novel [n]-paracyclophanes. The structural features and conformational biases of these molecules as evidenced by 1H-NMR and X-ray crystallography are highlighted along with molecular recognition studies.

Tübingen, Univ., Diss., 2002.

Techn. Hochsch., Diss., 2000--Aachen.

Universiẗat, Diss., 2000--Tübingen.

University, Diss., 2002--Tübingen. / Text engl.

In der vorliegenden Arbeit wird die Synthese von [2]Ferrocenophanen auf verschiedenen Wegen gezeigt. Neben der vollständigen Charakterisierung der Verbindungen wird auch deren Reaktivität untersucht. So wird gezeigt, dass mit den Elementen der Gruppe 16, sowie mit späten Übergangsmetallkomplexen eine Insertion in die Element-Element Bindung der Brücke statt finden kann. Darüber hinaus wird ausgehend von einem [2]Diboraferrocenophan eine katalytische Syntheseroute zur Diborierung von Alkinen entwickelt, sowohl unter homogenen als auch unter heterogen Bedingungen. Ausgehend von einem [2]Ferrocenophan wird eine neue Syntheseroute zur Darstellung von Ferrocenylboronsäureestern gezeigt. / Within this thesis, the synthesis of [2]ferrocenophanes is presented in different ways. Besides, the compounds are not only fully characterized, but also their reactivity is examined. It is shown, that on the addition of group 16 elements or late transition metal complexes, an insertion into the element-element bond can take place. Furthermore, starting from a [2]diboraferrocenophane, a synthetic protocol for the homogeneous and the heterogeneous catalyzed diboration of alkynes was developed. Starting from a [2]ferrocenophane, a new pathway for the synthesis of ferrocenyl boronic acids is presented.

Techn. Hochsch., Diss., 2001--Aachen.