Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy
The mechanism of the oxidation of arylsilanes to phenols has been investigated using (19)F NMR spectroscopy. The formation of silanols in these reactions results from a rapid background equilibrium between silanol and alkoxysilane; the relative rates of reaction of these species was evaluated by mod...
| Main Authors: | , , , |
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| Format: | Journal article |
| Language: | English |
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American Chemical Society
2017
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| _version_ | 1826303069413965824 |
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| author | Rayment, E Mekareeya, A Summerhill, N Anderson, E |
| author_facet | Rayment, E Mekareeya, A Summerhill, N Anderson, E |
| author_sort | Rayment, E |
| collection | OXFORD |
| description | The mechanism of the oxidation of arylsilanes to phenols has been investigated using (19)F NMR spectroscopy. The formation of silanols in these reactions results from a rapid background equilibrium between silanol and alkoxysilane; the relative rates of reaction of these species was evaluated by modeling of concentration profiles obtained through (19)F NMR spectroscopic reaction monitoring. Combining these results with a study of initial rates of phenol formation, and of substituent electronic effects, a mechanistic picture involving rapid and reversible formation of a pentavalent peroxide ate complex, prior to rate-limiting aryl migration, has evolved. |
| first_indexed | 2024-03-07T05:57:01Z |
| format | Journal article |
| id | oxford-uuid:eadf40ec-87f0-4c63-964e-bd465655bd30 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:57:01Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:eadf40ec-87f0-4c63-964e-bd465655bd302022-03-27T11:05:28ZMechanistic study of arylsilane oxidation through (19)F NMR spectroscopyJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:eadf40ec-87f0-4c63-964e-bd465655bd30EnglishSymplectic Elements at OxfordAmerican Chemical Society2017Rayment, EMekareeya, ASummerhill, NAnderson, EThe mechanism of the oxidation of arylsilanes to phenols has been investigated using (19)F NMR spectroscopy. The formation of silanols in these reactions results from a rapid background equilibrium between silanol and alkoxysilane; the relative rates of reaction of these species was evaluated by modeling of concentration profiles obtained through (19)F NMR spectroscopic reaction monitoring. Combining these results with a study of initial rates of phenol formation, and of substituent electronic effects, a mechanistic picture involving rapid and reversible formation of a pentavalent peroxide ate complex, prior to rate-limiting aryl migration, has evolved. |
| spellingShingle | Rayment, E Mekareeya, A Summerhill, N Anderson, E Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy |
| title | Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy |
| title_full | Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy |
| title_fullStr | Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy |
| title_full_unstemmed | Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy |
| title_short | Mechanistic study of arylsilane oxidation through (19)F NMR spectroscopy |
| title_sort | mechanistic study of arylsilane oxidation through 19 f nmr spectroscopy |
| work_keys_str_mv | AT raymente mechanisticstudyofarylsilaneoxidationthrough19fnmrspectroscopy AT mekareeyaa mechanisticstudyofarylsilaneoxidationthrough19fnmrspectroscopy AT summerhilln mechanisticstudyofarylsilaneoxidationthrough19fnmrspectroscopy AT andersone mechanisticstudyofarylsilaneoxidationthrough19fnmrspectroscopy |