Oxidation of isobutene and methylenecycloalkanes by palladium(II) acetate

Abstract

Reactions of isobutene, methylenecyclopentane, methylenecyclohexane and methylenecycloheptane with palladium acetate were studied in acetic acid at 30 to 80°. Two types of oxidation were identified: acetoxylation to allylic acetates (methylenecycloheptane) and oxidative coupling to dimers (isobutene and methylenecyclohexane). A mechanistic study indicated that the former was produced by thermal decomposition of the initially formed π-allylic complex. The latter process was presumed to proceed via an insertion of the olefin into the carbonpalladium bond in the acetoxypalladate adduct,{A figure is presented} followed by the elimination of the elements of acetic acid and palladium hydride. © 1974.