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Palladium-Catalyzed Cross-Coupling Reactions with Fluorinated Substrates: Mechanistic Insights into the Undesired Hydrodehalogenation of Aryl Halides

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posted on 22.02.2016, 04:57 by Meital Orbach, Joyanta Choudhury, Michal Lahav, Olena V. Zenkina, Yael Diskin-Posner, Gregory Leitus, Mark A. Iron, Milko E. van der Boom
We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon–carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of ArF–Pd­(II)–Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl–Br bond activation with fluorinated substrates and selective arene functionalization.