Allylic C-H acetoxylation with a 4,5-diazafluorenone-ligated palladium catalyst: a ligand-based strategy to achieve aerobic catalytic turnover

J Am Chem Soc. 2010 Nov 3;132(43):15116-9. doi: 10.1021/ja105829t.


Pd-catalyzed C-H oxidation reactions often require the use of oxidants other than O(2). Here we demonstrate a ligand-based strategy to replace benzoquinone with O(2) 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 O(2). Mechanistic studies have revealed that 1 facilitates C-O reductive elimination from a π-allyl-Pd(II) intermediate, thereby eliminating the requirement for benzoquinone in this key catalytic step.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Aerobiosis
  • Carbon / chemistry*
  • Catalysis
  • Fluorenes / chemistry*
  • Hydrogen / chemistry*
  • Ligands
  • Oxygen / chemistry
  • Palladium / chemistry*


  • 4,5-diazafluorenone
  • Fluorenes
  • Ligands
  • Palladium
  • Carbon
  • Hydrogen
  • Oxygen