PALLADIUM-CATALYZED ALLYLIC ACETOXYLATION OF OLEFINS USING HYDROGEN-PEROXIDE AS OXIDANT

A new and efficient system for the allylic acetoxylation of olefins ha s been developed, which consists of a palladium (II) catalyst and hydr ogen peroxide as oxidant in acetic acid. The acetoxylation reaction co mpetes with the epoxidation by the peracetic acid generated in situ in this system. Increase of the concentration of palladium catalyst and addition of benzoquinone (BQ), enhance the acetoxylation considerably. For the Pd(OAc)(2)-BQ-H2O2 system, more than 1000 turnover number cou ld be achieved in the acetoxylation of cyclohexene. Most internal and cyclic olefins tested gave the corresponding allylic acetates in fair to high yields. 1,3-Cyclohexadiene gave 1,4-diacetoxy-cyclohex-2-ene w hile 1,5-hexadiene afforded 3-acetoxy-methylenecyclopentane; 1,7-octad iene produced 1-octen-7-one and octan-2,7-dione. Terminal olefins gave methyl ketones in good yield with high turnover number both in the pr esence and absence of BQ. Possible mechanisms and involvement of palla dium peroxidic species in both the catalytic acetoxylation and ketoniz ation of olefins are discussed.