The first synthesis of (-)-asperpentyn and efficient syntheses of (+)-harveynone, (+)-epiepoformin and (-)-theobroxide.
A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived alpha-iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)-harveynone completed the first enantioselective synthesis of (-)-asperpentyn, another natural compound with antimicrobial activity.
Barros
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MT
Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa, Departamento de Química, Monte da Caparica, Portugal.
Maycock
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CD
Ventura
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MR
D000900:Anti-Bacterial Agents / Q000138:chemical synthesis*; D002855:Chromatography, Thin Layer; D003510:Cyclohexanes / Q000138:chemical synthesis*; D004852:Epoxy Compounds / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D011801:Quinic Acid / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism
D000900:Anti-Bacterial Agents; D003510:Cyclohexanes; D004852:Epoxy Compounds; D011801:Quinic Acid