Insights into Directing Group Ability in Palladium-Catalyzed C−H Bond Functionalization

This paper describes a detailed investigation of factors controlling the dominance of a directing group in Pd-catalyzed ligand-directed arene acetoxylation. Mechanistic studies, involving reaction kinetics, Hammett analysis, kinetic isotope effect experiments, and the kinetic order in oxidant, have...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2008-10, Vol.130 (40), p.13285-13293
Main Authors: Desai, Lopa V, Stowers, Kara J, Sanford, Melanie S
Format: Article
Language:English
Subjects:
Amides - chemistry
Carbon - chemistry
Catalysis
Enzyme Inhibitors - chemistry
Hydrogen - chemistry
Kinetics
Molecular Structure
Oximes - chemistry
Palladium - chemistry
Pyridines - chemistry
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Summary:This paper describes a detailed investigation of factors controlling the dominance of a directing group in Pd-catalyzed ligand-directed arene acetoxylation. Mechanistic studies, involving reaction kinetics, Hammett analysis, kinetic isotope effect experiments, and the kinetic order in oxidant, have been conducted for a series of different substrates. Initial rates studies of substrates bearing different directing groups showed that these transformations are accelerated by the use of electron-withdrawing directing groups. However, in contrast, under conditions where two directing groups are in competition with one another in the same reaction flask, substrates with electron-donating directing groups react preferentially. These results are discussed in the context of the proposed mechanism for Pd-catalyzed arene acetoxylation.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja8045519