Insights into Directing Group Ability in Palladium-Catalyzed C−H Bond Functionalization
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- 10 September 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 130 (40), 13285-13293
- https://doi.org/10.1021/ja8045519
Abstract
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.Keywords
This publication has 78 references indexed in Scilit:
- Thermodynamics of Pyridine Coordination in 1,4-Phenylene Bridged Bimetallic (Pd, Pt) Complexes Containing Two N,C,N‘ Motifs, 1,4-M2-[C6(CH2NR2)4-2,3,5,6]Inorganic Chemistry, 2006
- Intermolecular Amidation of Unactivated sp2 and sp3 C−H Bonds via Palladium-Catalyzed Cascade C−H Activation/Nitrene InsertionJournal of the American Chemical Society, 2006
- Combined C−H Functionalization/C−N Bond Formation Route to CarbazolesJournal of the American Chemical Society, 2005
- Palladium‐Catalyzed Asymmetric Iodination of Unactivated C-H Bonds under Mild ConditionsAngewandte Chemie International Edition, 2005
- Transition Metal Catalyzed Coupling Reactions under C−H ActivationAngewandte Chemie International Edition, 1999
- Oxidation of Heteroleptic Diarylpalladium Compounds withtert-Butyl Hydroperoxide. Substituent Effects in Aromatic Oxidation ReactionsOrganometallics, 1996
- Structure and nitrogen basicity of pyridine metal extractantsJournal of Radioanalytical and Nuclear Chemistry, 1996
- Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)Organometallics, 1994
- Rigid five- and six-membered C,N,N'-bound aryl-, benzyl-, and alkylorganopalladium complexes: sp2 vs. sp3 carbon-hydrogen activation during cyclopalladation and palladium(IV) intermediates in oxidative addition reactions with dihalogens and alkyl halidesOrganometallics, 1993
- Basicity and acidity of azoles: the annelation effect in azolesJournal of the American Chemical Society, 1988