Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons
Abstract The direct and selective coupling of benzenes with aliphatic hydrocarbons is a promising strategy for C(sp2)-C(sp3) bond formation using readily available starting materials, yet it remains a significant challenge. In this study, we have developed a simplified photochemical system that inco...
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| Format: | Article |
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Nature Portfolio
2023-10-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-42191-9 |
| _version_ | 1797558600839725056 |
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| author | Qian-Yu Li Shiyan Cheng Ziqi Ye Tao Huang Fuxing Yang Yu-Mei Lin Lei Gong |
| author_facet | Qian-Yu Li Shiyan Cheng Ziqi Ye Tao Huang Fuxing Yang Yu-Mei Lin Lei Gong |
| author_sort | Qian-Yu Li |
| collection | DOAJ |
| description | Abstract The direct and selective coupling of benzenes with aliphatic hydrocarbons is a promising strategy for C(sp2)-C(sp3) bond formation using readily available starting materials, yet it remains a significant challenge. In this study, we have developed a simplified photochemical system that incorporates catalytic amounts of iron(III) halides as multifunctional reagents and air as a green oxidant to address this synthetic problem. Under mild conditions, the reaction between a strong C(sp2)-H bond and a robust C(sp3)-H bond has been achieved, affording a broad range of cross-coupling products with high yields and commendable chemo-, site-selectivity. The iron halide acts as a multifunctional reagent that responds to visible light, initiates C-centered radicals, induces single-electron oxidation to carbocations, and participates in a subsequent Friedel-Crafts-type process. The gradual release of radical species and carbocation intermediates appears to be critical for achieving desirable reactivity and selectivity. This eco-friendly, cost-efficient approach offers access to various building blocks from abundant hydrocarbon feedstocks, and demonstrates the potential of iron halides in sustainable synthesis. |
| first_indexed | 2024-03-10T17:32:48Z |
| format | Article |
| id | doaj.art-9d71192a99d8488395b35a08bfdf1f78 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-10T17:32:48Z |
| publishDate | 2023-10-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-9d71192a99d8488395b35a08bfdf1f782023-11-20T09:57:15ZengNature PortfolioNature Communications2041-17232023-10-011411910.1038/s41467-023-42191-9Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbonsQian-Yu Li0Shiyan Cheng1Ziqi Ye2Tao Huang3Fuxing Yang4Yu-Mei Lin5Lei Gong6Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen UniversityAbstract The direct and selective coupling of benzenes with aliphatic hydrocarbons is a promising strategy for C(sp2)-C(sp3) bond formation using readily available starting materials, yet it remains a significant challenge. In this study, we have developed a simplified photochemical system that incorporates catalytic amounts of iron(III) halides as multifunctional reagents and air as a green oxidant to address this synthetic problem. Under mild conditions, the reaction between a strong C(sp2)-H bond and a robust C(sp3)-H bond has been achieved, affording a broad range of cross-coupling products with high yields and commendable chemo-, site-selectivity. The iron halide acts as a multifunctional reagent that responds to visible light, initiates C-centered radicals, induces single-electron oxidation to carbocations, and participates in a subsequent Friedel-Crafts-type process. The gradual release of radical species and carbocation intermediates appears to be critical for achieving desirable reactivity and selectivity. This eco-friendly, cost-efficient approach offers access to various building blocks from abundant hydrocarbon feedstocks, and demonstrates the potential of iron halides in sustainable synthesis.https://doi.org/10.1038/s41467-023-42191-9 |
| spellingShingle | Qian-Yu Li Shiyan Cheng Ziqi Ye Tao Huang Fuxing Yang Yu-Mei Lin Lei Gong Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons Nature Communications |
| title | Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons |
| title_full | Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons |
| title_fullStr | Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons |
| title_full_unstemmed | Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons |
| title_short | Visible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons |
| title_sort | visible light triggered selective c sp2 h c sp3 h coupling of benzenes with aliphatic hydrocarbons |
| url | https://doi.org/10.1038/s41467-023-42191-9 |
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