Proton-Abstraction Mechanism in the Palladium-Catalyzed Intramolecular Arylation: Substituent Effects
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- 27 April 2007
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 129 (21) , 6880-6886
- https://doi.org/10.1021/ja071034a
Abstract
The regioselectivity observed in the intramolecular palladium-catalyzed arylation of substituted bromobenzyldiarylmethanes as well as theoretical results demonstrate that the Pd-catalyzed arylation proceeds by a mechanism involving a proton abstraction by the carbonate, or a related basic ligand. The reaction is facilitated by electron-withdrawing substituents on the aromatic ring, which is inconsistent with an electrophilic aromatic-substitution mechanism. The more important directing effect is exerted by electron-withdrawing substituents ortho to the reacting site.Keywords
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