Allylic oxidation and first transformations of a key intermediate in the total synthesis of agarofuran sesquiterpenes

This paper describes the synthesis of polyhydroxylated decalinic systems through oxidative furan ring opening of 3-(2'-furyl)-2-methoxycarbonylcyclohexadione-4-monoethylene ketal 12 using dimethyl dioxirane (DMDO). The functionalisation of the decalinic product 5, aimed at the synthesis of antifeedant agarofuran sesquiterpenes according to our previously reported strategy, is demonstrated to occur with good stereochemical control of the introduced oxygenated functions, using as a key step an original allylic oxidation by DMDO. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).