Towards an Effective Synthesis of Functionalized Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane

by Martí Recort Fornals
Doctoral thesis
Date of Examination:2024-02-29
Date of issue:2024-03-14
Advisor:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Dietmar Stalke
Referee:Prof. Dr. Ricardo Mata
Referee:Prof. Dr. Johannes C. L. Walker
Referee:Prof. Dr. Anna Krawczuk
Referee:Prof. Dr. Daniel Obenchain
Persistent Address: http://dx.doi.org/10.53846/goediss-10395

 

 

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Abstract

English

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
 
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