Facilitating the Ferration of Aromatic Substrates through Intramolecular Sodium Mediation

Autor: Lewis C. H. Maddock, Max García-Melchor, Eva Hevia, Alan R. Kennedy, Manting Mu
Rok vydání: 2021
Předmět:
Zdroj: Angewandte Chemie (International Ed. in English)
Maddock, Lewis C. H.; Mu, Manting; Kennedy, Alan R.; García-Melchor, Max; Hevia, Eva (2021). Facilitating the Ferration of Aromatic Substrates through Intramolecular Sodium Mediation. Angewandte Chemie (International ed.), 60(28), pp. 15296-15301. Wiley-VCH 10.1002/anie.202104275
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202104275
Popis: Exploiting cooperative effects between Na and FeII centres present in tris(amide) ferrate complexes has led to the chemoselective ferration of pentafluorobenzene, benzene, toluene, anisole, and pyridine being realised at room temperature. The importance of this bimetallic partnership is demonstrated by neither the relevant sodium amide (NaHMDS or NaTMP) nor the FeII amide Fe(HMDS)2 efficiently metallating these substrates under the conditions of this study. By combining NMR studies with the isolation of key intermediates and DFT calculations, we offer a possible mechanism for how these reactions take place, uncovering a surprising reaction pathway in which the metals cooperate in a synchronised manner. Although the isolated products are formally the result of Fe‐H exchange, theoretical calculations indicate that the aromatic substrates undergo Na‐H exchange followed by fast intramolecular transmetallation to Fe, thus stabilizing the newly generated aryl fragment.
Combining iron with sodium in tris(amido) complexes has led to the selective ferration of non‐activated arenes being accomplished. A new cooperative mechanism is disclosed, whereby the sodium performs the metal‐H exchange and this is followed by a fast intramolecular trans‐metal trapping of the aryl anion by the iron centre.
Databáze: OpenAIRE
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