Aerobic C-H Acetoxylation of 8-Methylquinoline in PdII-Pyridinecarboxylic Acid Systems: Some Structure-Reactivity Relationships

Journal Article · Mon Sep 09 00:00:00 EDT 2013 · Organometallics

DOI:https://doi.org/10.1021/om400618n· OSTI ID:1105871

Wang, Daoyong ^[1]; Zavalij, Peter Y. ^[1]; Vedernikov, Andrei N. ^[1]

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1. Univ. of Maryland, College Park, MD (United States)

Catalytic oxidative C–H acetoxylation of 8-methylquinoline as a model substrate with O₂ as oxidant was performed using palladium(II) carboxylate catalysts derived from four different pyridinecarboxylic acids able to form palladium(II) chelates of different size. A comparison of the rates of the substrate C–H activation and the O₂ activation steps shows that the C–H activation step is rate-limiting, whereas the O₂ activation occurs at a much faster rate already at 20 °C. The chelate ring size and the chelate ring strain of the catalytically active species are proposed to be the key factors affecting the rate of the C–H activation.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• DOE Contract Number: SC0001298
• OSTI ID: 1105871
• Journal Information: Organometallics, Vol. 32, Issue 17; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

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