Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes
Selective C–C bond cleavage under ambient conditions is a challenging chemical transformation that can be a valuable tool for organic syntheses and macromolecular disassembly. Herein, we show that base metal vanadium photocatalysts can harvest visible light to effect the chemoselective C–C bond clea...
| Main Authors: | , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2018
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| Online Access: | https://hdl.handle.net/10356/89930 http://hdl.handle.net/10220/46441 |
| _version_ | 1826129005803208704 |
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| author | Gazi, Sarifuddin Ganguly, Rakesh Putra Moeljadi, Adhitya Mangala Hirao, Hajime Soo, Han Sen Ng, Wilson Kwok Hung |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Gazi, Sarifuddin Ganguly, Rakesh Putra Moeljadi, Adhitya Mangala Hirao, Hajime Soo, Han Sen Ng, Wilson Kwok Hung |
| author_sort | Gazi, Sarifuddin |
| collection | NTU |
| description | Selective C–C bond cleavage under ambient conditions is a challenging chemical transformation that can be a valuable tool for organic syntheses and macromolecular disassembly. Herein, we show that base metal vanadium photocatalysts can harvest visible light to effect the chemoselective C–C bond cleavage of lignin model compounds under ambient conditions. Lignin, a major aromatic constituent of non-food biomass, is an inexpensive, accessible source of fine chemical feedstocks such as phenols and aryl ethers. However, existing lignin degradation technologies are harsh and indiscriminately degrade valuable functional groups to produce intractable mixtures. The selective, photocatalytic depolymerization of lignin remains underexplored. In the course of our studies on lignin model compounds, we have uncovered a new C–C activation reaction that takes place under exceptionally mild conditions with high conversions. We present our fundamental studies on representative lignin model compounds, with the aim of expanding and generalizing the substrate scope in the future. Visible light is employed in the presence of earth-abundant vanadium oxo catalysts under ambient conditions. Selective C–C bond cleavage leads to valuable and functionally rich fine chemicals such as substituted aryl aldehydes and formates. Isotope labeling experiments, product analyses, and intermediate radical trapping, together with density functional theory studies, suggest a unique pathway that involves a photogenerated T1 state during the C–C bond cleavage reactions. Our study demonstrates a sustainable approach to harvest sunlight for an unusual, selective bond activation, which can potentially be applied in organic transformations and biomass valorization. |
| first_indexed | 2024-10-01T07:33:48Z |
| format | Journal Article |
| id | ntu-10356/89930 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:33:48Z |
| publishDate | 2018 |
| record_format | dspace |
| spelling | ntu-10356/899302023-02-28T19:36:12Z Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes Gazi, Sarifuddin Ganguly, Rakesh Putra Moeljadi, Adhitya Mangala Hirao, Hajime Soo, Han Sen Ng, Wilson Kwok Hung School of Physical and Mathematical Sciences Chemical Bonds DRNTU::Science::Chemistry Vanadium Compounds Selective C–C bond cleavage under ambient conditions is a challenging chemical transformation that can be a valuable tool for organic syntheses and macromolecular disassembly. Herein, we show that base metal vanadium photocatalysts can harvest visible light to effect the chemoselective C–C bond cleavage of lignin model compounds under ambient conditions. Lignin, a major aromatic constituent of non-food biomass, is an inexpensive, accessible source of fine chemical feedstocks such as phenols and aryl ethers. However, existing lignin degradation technologies are harsh and indiscriminately degrade valuable functional groups to produce intractable mixtures. The selective, photocatalytic depolymerization of lignin remains underexplored. In the course of our studies on lignin model compounds, we have uncovered a new C–C activation reaction that takes place under exceptionally mild conditions with high conversions. We present our fundamental studies on representative lignin model compounds, with the aim of expanding and generalizing the substrate scope in the future. Visible light is employed in the presence of earth-abundant vanadium oxo catalysts under ambient conditions. Selective C–C bond cleavage leads to valuable and functionally rich fine chemicals such as substituted aryl aldehydes and formates. Isotope labeling experiments, product analyses, and intermediate radical trapping, together with density functional theory studies, suggest a unique pathway that involves a photogenerated T1 state during the C–C bond cleavage reactions. Our study demonstrates a sustainable approach to harvest sunlight for an unusual, selective bond activation, which can potentially be applied in organic transformations and biomass valorization. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore) Published version 2018-10-26T02:42:08Z 2019-12-06T17:36:50Z 2018-10-26T02:42:08Z 2019-12-06T17:36:50Z 2015 Journal Article Gazi, S., Ng, W. K. H., Ganguly, R., Putra Moeljadi, A. M., Hirao, H., & Soo, H. S. (2015). Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes. Chemical Science, 6(12), 7130-7142. doi:10.1039/c5sc02923f 2041-6520 https://hdl.handle.net/10356/89930 http://hdl.handle.net/10220/46441 10.1039/C5SC02923F en Chemical Science © 2015 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. 13 p. application/pdf |
| spellingShingle | Chemical Bonds DRNTU::Science::Chemistry Vanadium Compounds Gazi, Sarifuddin Ganguly, Rakesh Putra Moeljadi, Adhitya Mangala Hirao, Hajime Soo, Han Sen Ng, Wilson Kwok Hung Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes |
| title | Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes |
| title_full | Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes |
| title_fullStr | Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes |
| title_full_unstemmed | Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes |
| title_short | Selective photocatalytic C–C bond cleavage under ambient conditions with earth abundant vanadium complexes |
| title_sort | selective photocatalytic c c bond cleavage under ambient conditions with earth abundant vanadium complexes |
| topic | Chemical Bonds DRNTU::Science::Chemistry Vanadium Compounds |
| url | https://hdl.handle.net/10356/89930 http://hdl.handle.net/10220/46441 |
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