22705-26-6Relevant articles and documents
Mechanism of the palladium-catalyzed arene C-H acetoxylation: A comparison of catalysts and ligand effects
Cook, Amanda K.,Sanford, Melanie S.
supporting information, p. 3109 - 3118 (2015/03/18)
This article describes detailed mechanistic studies focused on elucidating the impact of pyridine ligands on the Pd-catalyzed C-H acetoxylation of benzene. Three different catalysts, Pd(OAc)2, Pd(OAc)2/pyridine (1:1), and Pd(OAc)2/pyridine (1:2), are compared using a combination of mechanistic tools, including rate and order studies, Hammett analysis, detailed characterization of catalyst resting states, and isotope effects. The data from these experiments implicate C-H activation as the rate-limiting step in all cases. The major difference between the three catalysts is proposed to be the resting state of Pd. Under the reaction conditions, Pd(OAc)2 rests as an acetate bridged dimer, while the Pd(OAc)2/pyridine (1:2) catalyst rests as the monomer (pyridine)2Pd(OAc)2. In contrast, a variety of experiments suggest that the highly active catalyst generated from the 1:1 combination of Pd(OAc)2 and pyridine rests as the dimeric structure [(pyridine)Pd(OAc)2]2.
Remarkably high reactivity of Pd(OAc)2/pyridine catalysts: Nondirected C-H oxygenation of arenes
Emmert, Marion H.,Cook, Amanda K.,Xie, Yushu J.,Sanford, Melanie S.
supporting information; experimental part, p. 9409 - 9412 (2011/11/07)
Less is more: The rational optimization and general applicability of the catalytic system Pd(OAc)2/pyridine is described (see scheme). The catalyst shows excellent reactivity in the C-H oxygenation of simple aromatic substrates. The Pd/pyridine ratio is critical as the use of one equivalent of pyridine per Pd center leads to dramatic enhancements in both reactivity and site selectivity in comparison to Pd(OAc)2 alone.