Decarboxylative Strategies in Cobalt and Metallaphotoredox Catalysis: Approaches to Aroylation, Allylation, and Strain-Driven Reactivity

Herein, the design of distinct decarboxylative strategies to access synthetically valuable molecules is described. The primary goal has been to achieve environmentally friendly cross-coupling reactions that align with the principles of green chemistry. This was successfully achieved through the use of photoredox chemistry and catalysis with transition metals. Using these powerful tools, three main reactions were developed. The first is a direct decarboxylative Giese radical addition to β,β-disubstituted Michael acceptors, a reaction largely unexplored since its initial reports in the 1980s. By leveraging the four-membered ring strain release, this transformation is now feasible. The second involves the use of cobaloxime/photoredox cooperative catalysis to reinstall olefin functionality following a radical addition, yielding valuable α,β-unsaturated carbonyl compounds. Finally, a decarboxylative allylic alkylation using cobalt catalysis was developed, an area traditionally dominated by precious metals such as palladium. Together, these methodologies represent a significant advancement over existing methods and allow access to unprecedented molecules.

Grantor dc:publisher

University of Kansas

Year dc:date.issued

2025

Author dc:creator

• Diaz Hernandez, Rafael

Advisor dc:contributor.advisor

• Tunge, Jon A.

• Chemistry
• Allylation
• Aroylation
• Decarboxylative
• Strain

Statement dc:rights

• This item is protected by copyright and unless otherwise specified the copyright of this thesis/dissertation is held by the author.

Language dc:language.iso

en

Dc Identifier Other

https://www.proquest.com/LegacyDocView/DISSNUM/32167698

OAI identifier oai:identifier

oai:kuscholarworks.ku.edu:1808/37907