Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids
Abstract Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes with CO2 has attracted much attention for one-carbon homologation of alkynes, enabling rapid synthesis of propiolic acids. In co...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-57060-w |
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| author | Jin-Cheng Xu Jun-Ping Yue Min Pan Yi-Chi Chen Wei Wang Xi Zhou Wei Zhang Jian-Heng Ye Da-Gang Yu |
| author_facet | Jin-Cheng Xu Jun-Ping Yue Min Pan Yi-Chi Chen Wei Wang Xi Zhou Wei Zhang Jian-Heng Ye Da-Gang Yu |
| author_sort | Jin-Cheng Xu |
| collection | DOAJ |
| description | Abstract Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes with CO2 has attracted much attention for one-carbon homologation of alkynes, enabling rapid synthesis of propiolic acids. In contrast, the multi-carbons homologation of alkynes with CO2 to construct important non-conjugated alkynyl-containing acids has not been reported. Herein, we present alkynylcarboxylation of alkenes with CO2 via photoredox and copper dual catalysis. This protocol provides a direct and practical method to form valuable non-conjugated alkynyl acids from readily available alkynes, alkenes and CO2. Additionally, this approach also features mild (room temperature, 1 atm of CO2) and redox-neutral conditions, high atom and step economy, good functional group tolerance, and high selectivities. Moreover, diverse transformations of the β-alkynyl acid products and the rapid synthesis of bioactive molecule (GPR40/FFA1 agonist) further illustrate the synthetic utility of this methodology. |
| format | Article |
| id | doaj-art-c9302c36c8ac423494fe8bdbe5e20627 |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-c9302c36c8ac423494fe8bdbe5e206272025-08-20T03:10:56ZengNature PortfolioNature Communications2041-17232025-02-0116111010.1038/s41467-025-57060-wMetallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acidsJin-Cheng Xu0Jun-Ping Yue1Min Pan2Yi-Chi Chen3Wei Wang4Xi Zhou5Wei Zhang6Jian-Heng Ye7Da-Gang Yu8Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityWest China School of Public Health and West China Fourth Hospital, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityAbstract Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes with CO2 has attracted much attention for one-carbon homologation of alkynes, enabling rapid synthesis of propiolic acids. In contrast, the multi-carbons homologation of alkynes with CO2 to construct important non-conjugated alkynyl-containing acids has not been reported. Herein, we present alkynylcarboxylation of alkenes with CO2 via photoredox and copper dual catalysis. This protocol provides a direct and practical method to form valuable non-conjugated alkynyl acids from readily available alkynes, alkenes and CO2. Additionally, this approach also features mild (room temperature, 1 atm of CO2) and redox-neutral conditions, high atom and step economy, good functional group tolerance, and high selectivities. Moreover, diverse transformations of the β-alkynyl acid products and the rapid synthesis of bioactive molecule (GPR40/FFA1 agonist) further illustrate the synthetic utility of this methodology.https://doi.org/10.1038/s41467-025-57060-w |
| spellingShingle | Jin-Cheng Xu Jun-Ping Yue Min Pan Yi-Chi Chen Wei Wang Xi Zhou Wei Zhang Jian-Heng Ye Da-Gang Yu Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids Nature Communications |
| title | Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids |
| title_full | Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids |
| title_fullStr | Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids |
| title_full_unstemmed | Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids |
| title_short | Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids |
| title_sort | metallaphotoredox catalyzed alkynylcarboxylation of alkenes with co2 and alkynes for expedient access to β alkynyl acids |
| url | https://doi.org/10.1038/s41467-025-57060-w |
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