Acetoxylation

Pd-catalyzed C−H oxidation reactions often require the use of oxidants other than O2. Here we demonstrate a ligand-based strategy to replace benzoquinone with O2 as the stoichiometric oxidant in Pd-catalyzed allylic C−H acetoxylation. Use of 4,5-diazafluorenone (1) as an ancillary ligand for Pd(OAc)2 enables terminal alkenes to be converted to linear allylic acetoxylation products in good yields and selectivity under 1 atm O2. Mechanistic studies have revealed that 1 facilitates C−O reductive elimination from a π-allyl−PdIIintermediate, thereby eliminating the requirement for benzoquinone in this key catalytic step.

"Allylic C-H Acetoxylation with a 4,5-Diazafluorenone-Ligated Palladium Catalyst: A Ligand-Based Strategy to Achieve Aerobic Catalytic Turnover" 

Campbell, A. N.; White, P. B.; Guzei, I. A.; Stahl, S. S. J. Am. Chem. Soc.2010132, 15116–15119.  PDFSupporting Info.