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• Catalytic Transformations of CO₂ into Organic Compounds

  2024. Vu Duc Ha Phan.

  Avhandling (Dok)

  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.

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• Auto-Relay Catalysis for the Oxidative Carboxylation of Alkenes into Cyclic Carbonates by a MOF Catalyst

  2024. Ha Phan (et al.). Green Chemistry

  Artikel

  In this study, we present the preparation and application of a new manganoporphyrin Hf-MOF catalyst, Hf-PCN-222(Mn), for the direct oxidative carboxylation of alkenes with CO₂, leading to the effective formation of cyclic organic carbonates (COCs). In contrast to the conventional two-step process, this one-step methodology eliminates the need for the preparation, purification, and handling of epoxides. Hf-PCN-222(Mn) operates under very mild conditions, enabling the synthesis of a wide variety of COCs from alkenes (23 examples, up to 75% yield), as well as the chemoselective and size-selective carboxylation of dienes (7 examples, up to 61% yield). Additionally, we observed that Hf-PCN-222(Mn) could be recycled multiple times without significant loss of activity, providing insight into the sustainability of this approach.

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• Synthesis of Benzoic Acids from Electrochemically Reduced CO₂ Using Heterogeneous Catalysts

  2024. Ha Phan (et al.). ChemSusChem

  Artikel

  A method for the synthesis of benzoic acids from aryl iodides using two of the most abundant and sustainable feedstocks, carbon dioxide (CO₂) and water, is disclosed. Central to this method is an effective and selective electrochemical reduction of CO₂ (eCO₂RR) to CO, which mitigates unwanted dehalogenation reactions occurring when H₂ is produced via the hydrogen evolution reaction (HER). In a 3-compartment set-up, CO₂ was reduced to CO electrochemically by using a surface-modified silver electrode in aqueous electrolyte. The ex-situ generated CO further underwent hydroxycarbonylation of aryl iodides by MOF-supported palladium catalyst in excellent yields at room temperature. The method avoids the direct handling of hazardous CO gas and gives a wide range of benzoic acid derivatives. Both components of the tandem system can be recycled for several consecutive runs while keeping a high catalytic activity.

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• Photocatalytic Multicomponent Carboxylation of Olefins and Sulfinate Salts with ¹³CO₂

  2024. Julien R. Lyonnet (et al.). ACS Catalysis, 18633-18638

  Artikel

  Herein, we describe a photoinduced multicomponent catalytic carboxylation protocol that streamlines the access to ¹³C-labeled carboxylic acids from simple olefin precursors, sulfinate salts and ¹³CO₂. Site selectivity is dictated by the radical philicity of the starting precursors and reaction intermediates, resulting in either a four-component or a five-component endeavor. The method is characterized by its simplicity and flexibility across a wide number of coupling counterparts.

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