Towards an Effective Synthesis of Functionalized Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane
von Martí Recort Fornals
Datum der mündl. Prüfung:2024-02-29
Erschienen:2024-03-14
Betreuer:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Dietmar Stalke
Gutachter:Prof. Dr. Ricardo Mata
Gutachter:Prof. Dr. Johannes C. L. Walker
Gutachter:Prof. Dr. Anna Krawczuk
Gutachter:Prof. Dr. Daniel Obenchain
Dateien
Name:Recort-Fornals_Dissertation.pdf
Size:25.9Mb
Format:PDF
Zusammenfassung
Englisch
A reassessment of the Rh-catalyzed dimerization of norbornadiene to generate heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (HCTD), a carbocyclic cage compound, has been conducted introducing novel π-acceptor chelating phosphines. The usage of different ligands allowed for tuning of the reaction to selectively obtain different dimers derived from norbornadiene. After the reassessment of its synthesis, regioselective functionalization of HCTD was achieved through mild photofunctionalization processes involving the generation of radicals, allowing its reaction with a variety of electrophiles including examples of Minisci-type, Giese-type, and sulfonylation reactions, thus significantly expanding the functionalization toolkit for this scaffold. Difunctionalization of HCTD has also been obtained with regioselectivity by activating the less reactive position of the cage using directing groups in a Pd-catalyzed C–H functionalization process. Lastly, additional substitution patterns and preliminary studies to enable the enantioselective functionalization of HCTD have been presented.
Keywords: HCTD; cage compounds; photofunctionalization; C–H activation; phosphine; regioselectivity; aliphatic