Allylic Carboxylations and Lactonization Using Benzoquinone and Hydrogen Peroxide or tert-Butyl Hydroperoxide as Oxidants

Article abstract of DOI:10.1021/jo00098a035

Two new systems have been developed for catalytic carboxylation of alkenes.Both use palladium(II) as catalyst and benzoquinone as cocatalyst.In the first hydrogen peroxide was used as oxidant in acetic acid solution.Alkenes such as cyclohexene and 5-decene were converted cleanly to allylic acetates, but with 1-decene mainly the methyl ketone was formed.A diene such as 1,3-cyclohexadiene gave the diacetate while cis-1,2-divinylcyclohexane gave the cyclized monoacetate.In the second system, tert-butyl hydroperoxide was used as oxidant, permitting a wider choice of solvents and nucleophiles.Intramolecular reaction to lactones was possible in addition to allylic addition of acids such as benzoic, pivalic, and (S)-O-acetylmandelic acid.