Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Org Lett. 2013 Jan 4;15(1):6-9. doi: 10.1021/ol303071t. Epub 2012 Dec 18.
The first total syntheses of (-)-penicipyrone and (-)-tenuipyrone were accomplished enantioselectively in 12 steps with an 11% yield and 6 steps with a 28% yield from the known 4-((tert-butyldimethylsilyl)oxy)-cyclopent-2-enone, respectively, by developing a biomimetic bimolecular cascade cyclization featuring an intermolecular Michael addition/cyclo-(spiro-)ketalization sequence. The relative, absolute stereochemistry and carbon connectivity of penicipyrone was further confirmed by X-ray crystallographic analysis and comparison of optical rotations.
(-)-penicipyrone 和 (-)-tenuipyrone 的首次全合成分别通过生物模拟的双分子级联环化反应，以 11%的收率和 6 步 28%的收率，从已知的 4-((叔丁基二甲基甲硅烷基)氧基)-环戊-2-烯酮出发，实现了对映选择性地完成，其特征是分子间迈克尔加成/环（螺）缩酮化序列。通过 X 射线晶体学分析和旋光比较，进一步证实了 penicipyrone 的相对、绝对立体化学和碳连接性。
