20994-04-1Relevant articles and documents
Mechanism of Oxidative Activation of Fluorinated Aromatic Compounds by N-Bridged Diiron-Phthalocyanine: What Determines the Reactivity?
Colomban, Cédric,Tobing, Anthonio H.,Mukherjee, Gourab,Sastri, Chivukula V.,Sorokin, Alexander B.,de Visser, Sam P.
supporting information, p. 14320 - 14331 (2019/11/03)
The biodegradation of compounds with C?F bonds is challenging due to the fact that these bonds are stronger than the C?H bond in methane. In this work, results on the unprecedented reactivity of a biomimetic model complex that contains an N-bridged diiron-phthalocyanine are presented; this model complex is shown to react with perfluorinated arenes under addition of H2O2 effectively. To get mechanistic insight into this unusual reactivity, detailed density functional theory calculations on the mechanism of C6F6 activation by an iron(IV)-oxo active species of the N-bridged diiron phthalocyanine system were performed. Our studies show that the reaction proceeds through a rate-determining electrophilic C?O addition reaction followed by a 1,2-fluoride shift to give the ketone product, which can further rearrange to the phenol. A thermochemical analysis shows that the weakest C?F bond is the aliphatic C?F bond in the ketone intermediate. The oxidative defluorination of perfluoroaromatics is demonstrated to proceed through a completely different mechanism compared to that of aromatic C?H hydroxylation by iron(IV)-oxo intermediates such as cytochrome P450 Compound I.
Palladium-catalyzed C-F activation of polyfluoronitrobenzene derivatives in suzuki-miyaura coupling reactions
Cargill, Matthew R.,Sandford, Graham,Tadeusiak, Andrezj J.,Yufit, Dmitrii S.,Howard, Judith A. K.,Kilickiran, Pinar,Nelles, Gabrielle
scheme or table, p. 5860 - 5866 (2010/10/03)
Highly fluorinated nitrobenzene derivatives are suitable substrates for palladium-catalyzed C-F bond arylation using readily available palladium catalysts under both conventional heating and microwave conditions. Arylation occurs ortho to the nitro group offering a synthetic route to polyfluorinated 2-arylnitrobenzene systems. The regiochemistry of the arylation reactions suggests that there is a significant directing interaction between the nitro group and the incoming nucleophilic palladium catalyst which is facilitated by the presence of several fluorine atoms attached the ring. Investigations into the regioselectivity and reactivity of several tetrafluoro- and trifluoronitrobenzene derivatives provides further evidence for the highly nucleophilic character of the oxidative addition step in contrast to the concerted mechanism of more conventional Suzuki-Miyaura coupling reactions involving aryl iodides and bromides.
O-amino (thio) phenolcarboxylic acids and their preparation
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, (2008/06/13)
The invention relates to novel o-aminophenolcarboxylic acids, and o-aminothiophenolcarboxylic acids of the following structure: STR1 where A1 to A7 are--independently of one another--H, F, CH3, CF3, OCH3/s