Late-Stage Molecular Editing Enabled by Ketone Chain-Walking Isomerization.
| Autor: | Brägger Y; ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland., Green O; ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland., Bhawal BN; ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland.; School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, U.K., Morandi B; ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093 Zürich, Switzerland. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2023 Sep 13; Vol. 145 (36), pp. 19496-19502. Date of Electronic Publication: 2023 Aug 28. |
| DOI: | 10.1021/jacs.3c05680 |
| Abstrakt: | Herein, a method for the isomerization of ketones in a manner akin to the chain-walking reaction of alkenes is described. Widely available and inexpensive pyrrolidine and elemental sulfur are deployed as catalysts to achieve this reversible transformation. Key to the utility of this approach was the elucidation of a stereochemical model to determine the thermodynamically favored product of the reaction and the kinetic selectivity observed. With the distinct selectivity profile of our ketone chain-walking process, the isomerization of various steroids was demonstrated to rapidly access novel steroids with "unnatural" oxidation patterns. |
| Databáze: | MEDLINE |
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