Total Syntheses and Absolute Configuration Assignment of (+)-Sootepdienone, (−)-Jambolanin C, (−)-Jambolanin I, and (−) - Gibberodione
Total Syntheses and Absolute Configuration Assignment of (+)-Sootepdienone, (−)-Jambolanin C, (−)-Jambolanin I, and (−) - Gibberodione
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( )-Sootepdienone、(-)-Jambolanin C、(-)-Jambolanin I 和 (-)-Gibberodione 的全合成和绝对构型分配
DOI：
10.1021/acs.joc.0c02747
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Minehan, Thomas Gerard
中科院分区：
文献类型：
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作者：
Ng, Kevin;Khoury, Michael;Minehan, Thomas Gerard
从R-（+）-胡薄荷酮出发，经10步全合成了倍半萜类化合物（+）-胡薄荷二烯酮、（-）-jambolanin C、（-）-jambolanin I和（-）-赤霉二酮，并确定了天然产物的绝对构型。合成途径中的一个关键步骤涉及通过串联氧化裂解/分子内Horner-Wadsworth-Emmons反应将环状烯丙基膦酸酯的一碳环扩展为取代的环庚烯酮。
Total syntheses of the sesquiterpenes (+)-sootepdienone, (−)-jambolanin C, (−)-jambolanin I, and (−)-gibberodione have been accomplished in 10 steps each fromR-(+)-pulegone, allowing assignment of the absolute configuration of the natural products. A key step in the synthetic pathways involves the one-carbon ring expansion of a cyclic allylic phosphonate to a substituted cycloheptenone by a tandem oxidative cleavage/intramolecular Horner–Wadsworth–Emmons reaction.