The First Synthesis of (-)-Asperpentyn and Efficient Syntheses of (+)-Harveynone, (+)-Epiepoformin and (-)-Theobroxide

摘要

A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexand natural products has been developed. The enantisoelective syntheses of (-)-theogroxdie, a polyoxygenated cyclohexane natural products has been developed. The enantiselective synthesees of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-sily migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinoc acid. A thus derived a-iodoenoen was sugbjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar stragegy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also rpepared in enantiopure form and similarly, stereoselective reduction of (+)-haveynone completed teh first enantioselective syntehsis of (-)-asperpentyn, another natural compound with antimicrobial activity.