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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Bibliographic Details
Published in:Chemistry : a European journal 2023-03, Vol.29 (15), p.e202202963-n/a
Main Authors: Ogbu, Ikechukwu Martin, Kurtay, Gülbin, Badufle, Margaux, Robert, Frédéric, Lopez, Carlos Silva, Landais, Yannick
Format: Article
Language:English
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
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Summary: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.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202202963