Inverting the Selectivity of the Newman–Kwart Rearrangement via One Electron Oxidation at Room Temperature
The discovery that the Newman–Kwart rearrangement can be performed at room temperature by action of a simple and readily available oxidant, cerium ammonium nitrate, is described. The conditions give clean conversion when using electron-rich aromatic substrates, and the reactions are often quantitati...
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| Veröffentlicht in: | Journal of organic chemistry 2018-10, Vol.83 (19), p.12000-12006 |
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| container_end_page | 12006 |
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| container_issue | 19 |
| container_start_page | 12000 |
| container_title | Journal of organic chemistry |
| container_volume | 83 |
| creator | Pedersen, Stephan K Ulfkjær, Anne Newman, Madeleine N Yogarasa, Sarangki Petersen, Anne U Sølling, Theis I Pittelkow, Michael |
| description | The discovery that the Newman–Kwart rearrangement can be performed at room temperature by action of a simple and readily available oxidant, cerium ammonium nitrate, is described. The conditions give clean conversion when using electron-rich aromatic substrates, and the reactions are often quantitative. Computational studies support a reaction mechanism where the O-thiocarbamate is first oxidized to the radical cation, followed by nucleophilic attack by the ipso carbon of the aromatic system. |
| doi_str_mv | 10.1021/acs.joc.8b01800 |
| format | Article |
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| source | ACS Publications |
| title | Inverting the Selectivity of the Newman–Kwart Rearrangement via One Electron Oxidation at Room Temperature |
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