Tuning light-driven oxidation of styrene inside water-soluble nanocages
Abstract Selective functionalization of innate sp2 C-H bonds under ambient conditions is a grand synthetic challenge in organic chemistry. Here we combine host-guest charge transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tunin...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-45991-9 |
| _version_ | 1797274101786607616 |
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| author | Souvik Ghosal Ankita Das Debojyoti Roy Jyotishman Dasgupta |
| author_facet | Souvik Ghosal Ankita Das Debojyoti Roy Jyotishman Dasgupta |
| author_sort | Souvik Ghosal |
| collection | DOAJ |
| description | Abstract Selective functionalization of innate sp2 C-H bonds under ambient conditions is a grand synthetic challenge in organic chemistry. Here we combine host-guest charge transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration. We observe exclusive photocatalytic formation of benzaldehyde under excess O2 (>1 atm) while Markovnikov addition of water produced acetophenone in deoxygenated condition upon photoexcitation of confined styrene molecules inside a water-soluble cationic nanocage. Further by careful tuning of the nanocage size, electronics, and guest preorganization, we demonstrate rate enhancement of benzaldehyde formation and a complete switchover to the anti-Markovnikov product, 2-phenylethan-1-ol, in the absence of O2. Raman spectroscopy, 2D 1H-1H NMR correlation experiments, and transient absorption spectroscopy establish that the site-selective control on the confined photoredox chemistry originates from an optimal preorganization of styrene molecules inside the cavity. We envision that the demonstrated host-guest charge transfer photoredox paradigm in combination with green atom-transfer reagents will enable a broad range of sp2 carbon-site functionalization. |
| first_indexed | 2024-03-07T14:53:34Z |
| format | Article |
| id | doaj.art-7d8d129886234a30934868f318eb42e0 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-07T14:53:34Z |
| publishDate | 2024-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-7d8d129886234a30934868f318eb42e02024-03-05T19:32:40ZengNature PortfolioNature Communications2041-17232024-02-0115111610.1038/s41467-024-45991-9Tuning light-driven oxidation of styrene inside water-soluble nanocagesSouvik Ghosal0Ankita Das1Debojyoti Roy2Jyotishman Dasgupta3Department of Chemical Sciences, Tata Institute of Fundamental ResearchDepartment of Chemical Sciences, Tata Institute of Fundamental ResearchDepartment of Chemical Sciences, Tata Institute of Fundamental ResearchDepartment of Chemical Sciences, Tata Institute of Fundamental ResearchAbstract Selective functionalization of innate sp2 C-H bonds under ambient conditions is a grand synthetic challenge in organic chemistry. Here we combine host-guest charge transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration. We observe exclusive photocatalytic formation of benzaldehyde under excess O2 (>1 atm) while Markovnikov addition of water produced acetophenone in deoxygenated condition upon photoexcitation of confined styrene molecules inside a water-soluble cationic nanocage. Further by careful tuning of the nanocage size, electronics, and guest preorganization, we demonstrate rate enhancement of benzaldehyde formation and a complete switchover to the anti-Markovnikov product, 2-phenylethan-1-ol, in the absence of O2. Raman spectroscopy, 2D 1H-1H NMR correlation experiments, and transient absorption spectroscopy establish that the site-selective control on the confined photoredox chemistry originates from an optimal preorganization of styrene molecules inside the cavity. We envision that the demonstrated host-guest charge transfer photoredox paradigm in combination with green atom-transfer reagents will enable a broad range of sp2 carbon-site functionalization.https://doi.org/10.1038/s41467-024-45991-9 |
| spellingShingle | Souvik Ghosal Ankita Das Debojyoti Roy Jyotishman Dasgupta Tuning light-driven oxidation of styrene inside water-soluble nanocages Nature Communications |
| title | Tuning light-driven oxidation of styrene inside water-soluble nanocages |
| title_full | Tuning light-driven oxidation of styrene inside water-soluble nanocages |
| title_fullStr | Tuning light-driven oxidation of styrene inside water-soluble nanocages |
| title_full_unstemmed | Tuning light-driven oxidation of styrene inside water-soluble nanocages |
| title_short | Tuning light-driven oxidation of styrene inside water-soluble nanocages |
| title_sort | tuning light driven oxidation of styrene inside water soluble nanocages |
| url | https://doi.org/10.1038/s41467-024-45991-9 |
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