Since an allyl group can be transformed into various functional groups, the development of effective methods to construct an allyl substituted asymmetric quaternary center will be useful for the organic synthesis. Thus, we started to examine the possibility of "desymmetrization of 2,2-disubstituted cyclohexane-1,3-dione by intramolecular acetalization reaction". It was discovered that the carbonyl group was discriminated by the hydroxyl group derived from 2,2-diallylcyclohexane-1,3-dione by mono-dihydroxylation reaction of the olefin and produced two diastereomers in 6:1 ratio. The major product was successfully transformed to decalone derivative having an allyl group on the angular position. The good optical purity was observed by the asymmetric dihydroxylation reaction for the substrate having 2,2-bis-trans-2-butene unit. The application of this methodology to the natural product synthesis will be also reported.
