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Published on: August 12, 2019
Using Iron amides as Basic Reagents for Fluoroarene Metalation
1Departement für Chemie und Biochemie (DCBP), Universität Bern, Freiestrasse 3, CH-3012, Bern, Switzerland. kuziolajennifer@gmail.com.
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Fluoroarenes are important motifs in modern synthesis, yet regioselective C-H functionalization while preserving strong C-F bonds remains a significant challenge. Building on recent studies from our group, here we describe the potential of iron(II) amides to selectively promote regioselective mono- and di-ferration of a diverse range of fluoroaromatic substrates under mild conditions via Fe(II)-H exchange. Two alternative strategies are presented which include the use of a sodium ferrate which switches on heterobimetallic cooperation; and the development of a super basic iron amide containing TMP (2,2,6,6-tetramethylpiperidide) groups which allow for the efficient ferration of fluoroarenes under mild reaction conditions.
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Preparation of Amides
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...

