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 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.
Desai
Lopa V
LV
Chemistry Department, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, USA.
Stowers
Kara J
KJ
Sanford
Melanie S
MS
D000577:Amides / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D004791:Enzyme Inhibitors / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D010091:Oximes / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry
D000577:Amides; D004791:Enzyme Inhibitors; D010091:Oximes; D011725:Pyridines; D010165:Palladium; D002244:Carbon; D006859:Hydrogen
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