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Aerobic Acyloxylation of Allylic C-H Bonds Initiated by a Pd0 Precatalyst with 4,5-Diazafluoren-9-one as an Ancillary Ligand.

ABSTRACT: 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 Pd0 precatalyst under aerobic reaction conditions leads to oxidation of Pd0 by O2 in the presence of the desired carboxylic acid to generate a PdII 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.

SUBMITTER: Kozack CV

PROVIDER: S-EPMC7641472 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Aerobic Acyloxylation of Allylic C-H Bonds Initiated by a Pd0 Precatalyst with 4,5-Diazafluoren-9-one as an Ancillary Ligand.

Kozack Caitlin V CV Sowin Jennifer A JA Jaworski Jonathan N JN Iosub Andrei V AV Stahl Shannon S SS

ChemSusChem 20190605 13

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 Pd0 precatalyst under aerobic reaction conditions leads to oxidation of Pd0 by O2 in the presence of the desired carboxylic acid to generate a PdII dicarboxylate that promotes acyloxylation of the allylic C-H bond. Good-to-exc ...[more]

PMID: 31107593

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