Palladium-Catalyzed Cross-Coupling Reactions with Fluorinated Substrates: Mechanistic Insights into the Undesired Hydrodehalogenation of Aryl Halides
datasetposted on 22.02.2016, 04:57 authored 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.