Catalytic Transformations of CO2 into Organic Compounds
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]
Carbon dioxide (CO2) is present in our atmosphere as the fourth most abundant gas. The non-toxicity and non-flammability of CO2 makes it an attractive C1-synthon in organic synthesis. This thesis aims to develop catalytic transformations to utilize CO2 in the preparation of organic compounds, namely carboxylic acids and cyclic carbonates. The developed methods center around photoredox chemistry, electrochemistry, homogeneous catalysis, and heterogeneous catalysis. Synthesis of carbon-isotope-labeled organic compounds from isotopic CO2 which are of great importance in medicinal chemistry was also presented.
Due to the inertness of CO2, activation of either CO2 or other starting materials by photocatalysis or electrocatalysis facilitates the incorporation of CO2 into organic compounds. By using a photoredox catalyst under visible light irradiation, highly reactive carbanions can be formed from common feedstocks, such as sulfinate salts and alkenes. The electron-dense carbanions readily react with 13CO2 to yield 13C-labeled aliphatic carboxylic acids. On the contrary, CO2 can be electrochemically reduced to the more reactive CO, which can readily undergo palladium-catalyzed hydroxycarbonylation with aryl iodides to yield benzoic acids. In this work, tandem reactions based on the use of recyclable heterogeneous catalysis have been developed for this transformation.
Epoxides are ring-strained molecules that can undergo cycloaddition reactions with CO2 to yield cyclic carbonates. In this thesis, a stereospecific catalytic approach for accessing 13C- and 14C-labeled chiral cyclic carbonates using near stoichiometric amount of CO2 was developed. The labeled chiral cyclic carbonates serve as precursors for the synthesis of isotope-labeled pharmaceuticals. Furthermore, an auto-relay heterogeneous catalysis approach was developed to obtain epoxides from readily available alkenes in a chemoselective manner, which can further react with CO2 to form cyclic carbonates.
Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2024. , p. 96
Keywords [en]
Catalysis, Carbon dioxide, Photochemistry, Electrochemistry, Metal-Organic Frameworks
National Category
Organic Chemistry Materials Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-232316ISBN: 978-91-8014-881-8 (print)ISBN: 978-91-8014-882-5 (electronic)OAI: oai:DiVA.org:su-232316DiVA, id: diva2:1888469
Public defence
2024-09-26, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16B, Stockholm, 13:00 (English)
Opponent
Supervisors
2024-09-032024-08-132024-10-03Bibliographically approved