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Detection of Palladium(I) in Aerobic Oxidation Catalysis
Author(s) -
Jaworski Jonathan N.,
McCann Scott D.,
Guzei Ilia A.,
Stahl Shan S.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201700345
Subject(s) - palladium , chemistry , catalysis , allylic rearrangement , reactivity (psychology) , intramolecular force , ligand (biochemistry) , coupling reaction , combinatorial chemistry , medicinal chemistry , stereochemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
Palladium(II)‐catalyzed oxidation reactions exhibit broad utility in organic synthesis; however, they often feature high catalyst loading and low turnover numbers relative to non‐oxidative cross‐coupling reactions. Insights into the fate of the Pd catalyst during turnover could help to address this limitation. Herein, we report the identification and characterization of a dimeric Pd I species in two prototypical Pd‐catalyzed aerobic oxidation reactions: allylic C−H acetoxylation of terminal alkenes and intramolecular aza‐Wacker cyclization. Both reactions employ 4,5‐diazafluoren‐9‐one (DAF) as an ancillary ligand. The dimeric Pd I complex, [Pd I (μ‐DAF)(OAc)] 2 , which features two bridging DAF ligands and two terminal acetate ligands, has been characterized by several spectroscopic methods, as well as single‐crystal X‐ray crystallography. The origin of this Pd I complex and its implications for catalytic reactivity are discussed.