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PIDA‐mediated Oxidative Decarboxylation of Oxamic Acids. The Role of Radical Acidity Enhancement
The PIDA‐mediated oxidative decarboxylation of oxamic acids in the presence of alcohols is shown to afford the corresponding urethanes under thermal conditions. Computational and experimental mechanistic exploration allows to rationalize the different reactivity of PIDA as compared to related cyclic...
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| Published in: | Chemistry : a European journal 2023-03, Vol.29 (15), p.e202202963-n/a |
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| Main Authors: | , , , , , |
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| Language: | English |
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| cited_by | cdi_FETCH-LOGICAL-c4473-91ab72fe41ce6ca79d741a251cc18db5501a9502255f5d9277bf386a1cdff8d73 |
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| cites | cdi_FETCH-LOGICAL-c4473-91ab72fe41ce6ca79d741a251cc18db5501a9502255f5d9277bf386a1cdff8d73 |
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| container_issue | 15 |
| container_start_page | e202202963 |
| container_title | Chemistry : a European journal |
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| creator | Ogbu, Ikechukwu Martin Kurtay, Gülbin Badufle, Margaux Robert, Frédéric Lopez, Carlos Silva Landais, Yannick |
| description | The PIDA‐mediated oxidative decarboxylation of oxamic acids in the presence of alcohols is shown to afford the corresponding urethanes under thermal conditions. Computational and experimental mechanistic exploration allows to rationalize the different reactivity of PIDA as compared to related cyclic BI‐OAc and highlights the importance of the enhanced acidity of the proton in the carbamoyl radical intermediate.
An expedient thermal protocol to decarboxylate oxamic acids is found to have contrasting behaviour with its photochemical alternative. The enhanced radical acidity of a carbamoyl intermediate is shown to be key in the reaction mechanism. |
| doi_str_mv | 10.1002/chem.202202963 |
| format | article |
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| ispartof | Chemistry : a European journal, 2023-03, Vol.29 (15), p.e202202963-n/a |
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| language | eng |
| recordid | cdi_hal_primary_oai_HAL_hal_04271835v1 |
| source | Wiley-Blackwell Read & Publish Collection |
| subjects | Acidity Alcohols Carbamate compounds carbamoyl radical Chemical Sciences Chemistry Computer applications Decarboxylation DFT hypervalent iodine isocyanate or physical chemistry Organic chemistry Oxamic acids Theoretical and urethane Urethanes |
| title | PIDA‐mediated Oxidative Decarboxylation of Oxamic Acids. The Role of Radical Acidity Enhancement |
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