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Spontaneous α‐C−H Carboxylation of Ketones by Gaseous CO2 at the Air‐water Interface of Aqueous Microdroplets
We present a catalyst‐free route for the reduction of carbon dioxide integrated with the formation of a carbon‐carbon bond at the air/water interface of negatively charged aqueous microdroplets, at ambient temperature. The reactions proceed through carbanion generation at the α‐carbon of a ketone fo...
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| Published in: | Angewandte Chemie 2024-07, Vol.136 (27), p.n/a |
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| Main Authors: | , , , , , , , |
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| Language: | English |
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| container_end_page | n/a |
| container_issue | 27 |
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| container_title | Angewandte Chemie |
| container_volume | 136 |
| creator | Basuri, Pallab Mukhopadhyay, Sinchan Reddy, K. S. S. V. Prasad Unni, Keerthana Spoorthi, B. K. Shantha Kumar, Jenifer Yamijala, Sharma S. R. K. C. Pradeep, Thalappil |
| description | We present a catalyst‐free route for the reduction of carbon dioxide integrated with the formation of a carbon‐carbon bond at the air/water interface of negatively charged aqueous microdroplets, at ambient temperature. The reactions proceed through carbanion generation at the α‐carbon of a ketone followed by nucleophilic addition to CO2. Online mass spectrometry reveals that the product is an α‐ketoacid. Several factors, such as the concentration of the reagents, pressure of CO2 gas, and distance traveled by the droplets, control the kinetics of the reaction. Theoretical calculations suggest that water in the microdroplets facilitates this unusual chemistry. Furthermore, such a microdroplet strategy has been extended to seven different ketones. This work demonstrates a green pathway for the reduction of CO2 to useful carboxylated organic products.
Charged aqueous microdroplets facilitate carboxylation at α‐C−H position of ketones by gaseous CO2 at the air–water Interface. |
| doi_str_mv | 10.1002/ange.202403229 |
| format | article |
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Charged aqueous microdroplets facilitate carboxylation at α‐C−H position of ketones by gaseous CO2 at the air–water Interface.</description><subject>Air temperature</subject><subject>Air-water interface</subject><subject>Ambient temperature</subject><subject>carbanion</subject><subject>Carbon dioxide</subject><subject>Carbon dioxide reduction</subject><subject>Carboxylation</subject><subject>Catalysts</subject><subject>Ketones</subject><subject>Mass spectrometry</subject><subject>Mass spectroscopy</subject><subject>microdroplet chemistry</subject><subject>Reagents</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNo9kLFOwzAQhi0EEqWwMltiTrEdJ47HKCptRaFD2S0nsSFViIPtqmRjZES8CS_CQ_RJSFvU5U4nff_d6QPgGqMRRojcyuZZjQgiFIWE8BMwwBHBQcgidgoGCFEaJITyc3Dh3AohFBPGB8AvW9N42SizdvD3Z_vxlW0_v6cwkzY3710tfWUaaDS8V940ysG8gxPp9ni2IFB66F8UTCvbRzfSKwtnTV-1LNQulr6t9-xDVVhTWtPWyrtLcKZl7dTVfx-C5d34KZsG88VklqXzoGUJDxSKJE5oHBWsQFxTXZY5K1hMOUU0zrlEBCckiXnEIk10zxGGCyJVQkqtwnAIbg5bW2v6L5wXK7O2TX9QhIhhilkvqqf4gdpUtepEa6tXaTuBkdhJFTup4ihVpI-T8XEK_wBP1XEV</recordid><startdate>20240701</startdate><enddate>20240701</enddate><creator>Basuri, Pallab</creator><creator>Mukhopadhyay, Sinchan</creator><creator>Reddy, K. 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C.</au><au>Pradeep, Thalappil</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Spontaneous α‐C−H Carboxylation of Ketones by Gaseous CO2 at the Air‐water Interface of Aqueous Microdroplets</atitle><jtitle>Angewandte Chemie</jtitle><date>2024-07-01</date><risdate>2024</risdate><volume>136</volume><issue>27</issue><epage>n/a</epage><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>We present a catalyst‐free route for the reduction of carbon dioxide integrated with the formation of a carbon‐carbon bond at the air/water interface of negatively charged aqueous microdroplets, at ambient temperature. The reactions proceed through carbanion generation at the α‐carbon of a ketone followed by nucleophilic addition to CO2. Online mass spectrometry reveals that the product is an α‐ketoacid. Several factors, such as the concentration of the reagents, pressure of CO2 gas, and distance traveled by the droplets, control the kinetics of the reaction. Theoretical calculations suggest that water in the microdroplets facilitates this unusual chemistry. Furthermore, such a microdroplet strategy has been extended to seven different ketones. This work demonstrates a green pathway for the reduction of CO2 to useful carboxylated organic products.
Charged aqueous microdroplets facilitate carboxylation at α‐C−H position of ketones by gaseous CO2 at the air–water Interface.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.202403229</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0003-3174-534X</orcidid></addata></record> |
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| language | eng |
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| subjects | Air temperature Air-water interface Ambient temperature carbanion Carbon dioxide Carbon dioxide reduction Carboxylation Catalysts Ketones Mass spectrometry Mass spectroscopy microdroplet chemistry Reagents |
| title | Spontaneous α‐C−H Carboxylation of Ketones by Gaseous CO2 at the Air‐water Interface of Aqueous Microdroplets |
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