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Palladium/Norbornene-Catalyzed ortho Aliphatic Acylation with Mixed Anhydride: Selectivity and Reactivity
Shibo Xu1, Julong Jiang1, Linlin Ding1
1Department of Chemistry and Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China , 96 Jinzhai Road, Hefei, Anhui 230026, P. R. China.
Abstract:
A palladium/norbornene-catalyzed ortho acylation for the efficient synthesis of functionalized alkyl aryl ketones is reported. Studies on the electronic and steric properties of mixed aryl anhydrides indicated that the cross-coupling favored with the electron-enriched aryl acyl group. DFT calculation on the oxidative addition of Pd(II) with 2,4,6-(Cl)3C6H2CO2C(O)Ph suggested that 2,4,6-(Cl)3C6H2C(O)-O bond cleavage was more kinetically disfavored than that of the PhC(O)-O bond by 11.7 kJ/mol.
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