Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy
A one-pot multicomponent green process is investigated for the synthesis of perfluoroalkylated cyclic carbonate which merges the photo-promoted Atom Transfer Radical Addition (ATRA) of a perfluoroalkyl iodide (Rf-I) onto allyl alcohols with the Lewis-base-promoted carboxylative cyclization. The evol...
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MDPI AG
2023-05-01
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| Online Access: | https://www.mdpi.com/2073-4344/13/6/939 |
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| author | Joseph Grondin Christian Aupetit Jean-Marc Vincent Thierry Tassaing |
| author_facet | Joseph Grondin Christian Aupetit Jean-Marc Vincent Thierry Tassaing |
| author_sort | Joseph Grondin |
| collection | DOAJ |
| description | A one-pot multicomponent green process is investigated for the synthesis of perfluoroalkylated cyclic carbonate which merges the photo-promoted Atom Transfer Radical Addition (ATRA) of a perfluoroalkyl iodide (Rf-I) onto allyl alcohols with the Lewis-base-promoted carboxylative cyclization. The evolution of the complex mixture during the reaction was monitored by in situ ATR-IR and Raman spectroscopies that provided insights into the reaction mechanism. The effect on the kinetics and the carbonate yields of key parameters such as the stoichiometry of reagents, the nature of the Lewis base and the solvent, the temperature and the pressure were evaluated. It was found that high yields were obtained using strong Lewis bases that played both the role of activating the allyl alcohol for the generation of the allyl carbonate in the presence of CO<sub>2</sub> and promoting the ATRA reaction through the activation of C<sub>4</sub>F<sub>9</sub>I by halogen bonding. This protocol was also extended to various unsaturated alcohols. |
| first_indexed | 2024-03-11T02:39:55Z |
| format | Article |
| id | doaj.art-98a8073db0684041a9cd3e616a3e9ec7 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-11T02:39:55Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-98a8073db0684041a9cd3e616a3e9ec72023-11-18T09:41:29ZengMDPI AGCatalysts2073-43442023-05-0113693910.3390/catal13060939Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR SpectroscopyJoseph Grondin0Christian Aupetit1Jean-Marc Vincent2Thierry Tassaing3Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351, Cours de la Libération, F-33405 Talence, FranceInstitut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351, Cours de la Libération, F-33405 Talence, FranceInstitut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351, Cours de la Libération, F-33405 Talence, FranceInstitut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351, Cours de la Libération, F-33405 Talence, FranceA one-pot multicomponent green process is investigated for the synthesis of perfluoroalkylated cyclic carbonate which merges the photo-promoted Atom Transfer Radical Addition (ATRA) of a perfluoroalkyl iodide (Rf-I) onto allyl alcohols with the Lewis-base-promoted carboxylative cyclization. The evolution of the complex mixture during the reaction was monitored by in situ ATR-IR and Raman spectroscopies that provided insights into the reaction mechanism. The effect on the kinetics and the carbonate yields of key parameters such as the stoichiometry of reagents, the nature of the Lewis base and the solvent, the temperature and the pressure were evaluated. It was found that high yields were obtained using strong Lewis bases that played both the role of activating the allyl alcohol for the generation of the allyl carbonate in the presence of CO<sub>2</sub> and promoting the ATRA reaction through the activation of C<sub>4</sub>F<sub>9</sub>I by halogen bonding. This protocol was also extended to various unsaturated alcohols.https://www.mdpi.com/2073-4344/13/6/939CO<sub>2</sub> organocatalysisphoto-promoted ATRAcyclic carbonates |
| spellingShingle | Joseph Grondin Christian Aupetit Jean-Marc Vincent Thierry Tassaing Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy Catalysts CO<sub>2</sub> organocatalysis photo-promoted ATRA cyclic carbonates |
| title | Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy |
| title_full | Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy |
| title_fullStr | Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy |
| title_full_unstemmed | Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy |
| title_short | Cyclic Carbonates through the Photo-Induced Carboxylative Cyclization of Allylic Alcohol with CO<sub>2</sub>: A Comprehensive Kinetic Study of the Reaction Mechanism by In Situ ATR-IR Spectroscopy |
| title_sort | cyclic carbonates through the photo induced carboxylative cyclization of allylic alcohol with co sub 2 sub a comprehensive kinetic study of the reaction mechanism by in situ atr ir spectroscopy |
| topic | CO<sub>2</sub> organocatalysis photo-promoted ATRA cyclic carbonates |
| url | https://www.mdpi.com/2073-4344/13/6/939 |
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