Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O)
It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in the superbase suspension KOH/DMSO(H<sub>2</sub>O) at 85 °C for 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates that were earlier inaccessible in a yie...
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2025-03-01
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| Series: | Molecules |
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| author | Vladimir A. Kuimov Svetlana F. Malysheva Natalia A. Belogorlova Ruslan I. Fattakhov Alexander I. Albanov Irina Yu. Bagryanskaya Nikolay I. Tikhonov Boris A. Trofimov |
| author_facet | Vladimir A. Kuimov Svetlana F. Malysheva Natalia A. Belogorlova Ruslan I. Fattakhov Alexander I. Albanov Irina Yu. Bagryanskaya Nikolay I. Tikhonov Boris A. Trofimov |
| author_sort | Vladimir A. Kuimov |
| collection | DOAJ |
| description | It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in the superbase suspension KOH/DMSO(H<sub>2</sub>O) at 85 °C for 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates that were earlier inaccessible in a yield of up to 45%. The ESR data demonstrate that unlike previously published phosphorylation with elemental phosphorus, this new phosphorylation reaction proceeds via a single electron transfer from polyphospide anions to diaryl(hetaryl)ketones. This is the first example of the C-O-P bond generation during the phosphorylation with elemental phosphorus in strongly basic media, which usually provides C-P bond formation. |
| format | Article |
| id | doaj-art-0d3bbd62384d4c0eb773ff0d2a8b9e8e |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-0d3bbd62384d4c0eb773ff0d2a8b9e8e2025-08-20T03:43:20ZengMDPI AGMolecules1420-30492025-03-01306136710.3390/molecules30061367Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O)Vladimir A. Kuimov0Svetlana F. Malysheva1Natalia A. Belogorlova2Ruslan I. Fattakhov3Alexander I. Albanov4Irina Yu. Bagryanskaya5Nikolay I. Tikhonov6Boris A. Trofimov7A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, RussiaIt was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in the superbase suspension KOH/DMSO(H<sub>2</sub>O) at 85 °C for 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates that were earlier inaccessible in a yield of up to 45%. The ESR data demonstrate that unlike previously published phosphorylation with elemental phosphorus, this new phosphorylation reaction proceeds via a single electron transfer from polyphospide anions to diaryl(hetaryl)ketones. This is the first example of the C-O-P bond generation during the phosphorylation with elemental phosphorus in strongly basic media, which usually provides C-P bond formation.https://www.mdpi.com/1420-3049/30/6/1367red phosphorusstrong basebis(benzhydryl)phosphatesbenzophenonesingle-electron transfer |
| spellingShingle | Vladimir A. Kuimov Svetlana F. Malysheva Natalia A. Belogorlova Ruslan I. Fattakhov Alexander I. Albanov Irina Yu. Bagryanskaya Nikolay I. Tikhonov Boris A. Trofimov Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O) Molecules red phosphorus strong base bis(benzhydryl)phosphates benzophenone single-electron transfer |
| title | Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O) |
| title_full | Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O) |
| title_fullStr | Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O) |
| title_full_unstemmed | Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O) |
| title_short | Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H<sub>2</sub>O) |
| title_sort | straightforward superbase mediated reductive o phosphorylation of aromatic and heteroaromatic ketones with red phosphorus in the superbase suspension koh dmso h sub 2 sub o |
| topic | red phosphorus strong base bis(benzhydryl)phosphates benzophenone single-electron transfer |
| url | https://www.mdpi.com/1420-3049/30/6/1367 |
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