ISBN 9783843955614

978-3-8439-5561-4, Reihe Organische Chemie

Lukas Benedikt Miller
Carbonylation as a Key Step in New Tandem Reactions

396 Seiten, Dissertation Albert-Ludwigs-Universität Freiburg im Breisgau (2024), Softcover, A5

Zusammenfassung / Abstract

This thesis explores the use of the hydroformylation reaction in tandem syntheses.

The first project focused on the synthesis of diindolylmethanes through a tandem hydroformylation-Friedel-Crafts reaction sequence, starting from alkenes, allenes, and alkynes to give aldehyde intermediates, followed by an in-situ Friedel-Crafts reaction with indole nucleophiles. Four new diindolylmethanes were synthesized, expanding the scope to 21 compounds with various functional groups, useful for applications in medicinal chemistry, such as cancer treatment.

The second project, derived from the diindolylmethane work, developed a method for synthesizing BODIPY dyes. The process involved a five-step reaction sequence starting from alkenes or aryl bromides, forming aldehyde intermediates via rhodium or palladium-catalyzed reactions. The aldehyde was activated by a squaramide organocatalyst for reaction with pyrrole nucleophiles. This method led to 55 meso-alkyl and -aryl BODIPYs with various substitution patterns, achieving higher yields compared to previous methods. The approach could be beneficial for applications in biochemistry, materials science, and therapy.

The third project refined the hydroformylation process for meso-alkyl BODIPYs to address the drawbacks of using high-pressure autoclaves. A simplified and environmentally benign method using a CO/H2 balloon and a simple Schlenk tube was developed, while improving the efficiency of the reaction. This new method allowed for the synthesis of 23 meso-alkyl BODIPYs with up to 67% yield, including compounds with amino acids bearing terminal alkenes. This refinement enabled easier access to meso-alkyl BODIPYs for various applications.