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Aerobic Acyloxylation of Allylic C−H Bonds Initiated by a Pd 0 Precatalyst with 4,5‐Diazafluoren‐9‐one as an Ancillary Ligand
Author(s) -
Kozack Caitlin V.,
Sowin Jennifer A.,
Jaworski Jonathan N.,
Iosub Andrei V.,
Stahl Shan S.
Publication year - 2019
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201900727
Subject(s) - allylic rearrangement , chemistry , alkene , catalysis , palladium , ligand (biochemistry) , reagent , acetic acid , medicinal chemistry , carboxylic acid , polymer chemistry , organic chemistry , receptor , biochemistry
Palladium‐catalyzed allylic C−H oxidation has been widely studied, but most precedents use acetic acid as the coupling partner. In this study, a method compatible with diverse carboxylic acid partners has been developed. Use of a Pd 0 precatalyst under aerobic reaction conditions leads to oxidation of Pd 0 by O 2 in the presence of the desired carboxylic acid to generate a Pd II dicarboxylate that promotes acyloxylation of the allylic C−H bond. Good‐to‐excellent yields are obtained with a roughly 1:1 ratio of the alkene and carboxylic acid reagents. Optimized reaction conditions employ 4,5‐diazafluoren‐9‐one (DAF) as a ligand, in combination with a quinone/iron phthalocyanine cocatalyst system to support aerobic catalytic turnover.