ISBN 978-3-8439-4862-3

978-3-8439-4862-3, Reihe Organische Chemie

Felix Krupp
Synthese von Tetraaryladamantanen und deren Anwendung in der Strukturaufklärung

203 Seiten, Dissertation Universität Stuttgart (2021), Softcover, A5

Zusammenfassung / Abstract

This thesis focuses on the synthesis of new tetraaryladamantanes (TAAs) and their use for the co-crystallization of small organic molecules. Detailed co-crystallization studies using 1,3,5,7-tetrakis(2,4-dimethoxyphenyl) adamantane (TDA) and 1,3,5,7-tetrakis(2,4-diethoxyphenyl)adamantane (TEO) were successfully performed in the Richert research group over the last years. The TAAs potential for possible applications has been successfully demonstrated for the stabilization of reactive molecules and the uptake of solvents from the gas phase. A special motivation of this work was to use tetraaryladamantanes as chaperones for elucidating structures of small organic molecules and open up a new application field for this compound class.

In this work, tetraaryladamantes were used for X-ray based structures elucidation. With this new thermal co-crystallization method, 33 compounds were co-crystallized and their structures were determined successfully. In this study, 23 of the 33 compounds were chiral molecules, and for 21 of them their absolute configuration was determined. In most of the cases, a crystal structure was obtained within 48 hours, while known (co-)crystallization methods, like crystalline sponges, typically require one or several weeks to achieve structure elucidation. The scope of analytes included hard to crystallize oily natural products, some of which had not been (co-)crystallized before. In addition, the determination of relative configurations of propargyl cyclopropanes was successfully demonstrated in a collaboration. In summary, this new thermal cocrystallization method using tetraaryladamantanes and small, liquid, hard to crystallize molecules, is a rapid, inexpensive and convenient alternative to known (co-)crystallization methods. It may find applications in the co-crystallization of newly synthesized, but hard to crystallize small molecules.