Translation of a Polar Biogenesis Proposal into a Radical Synthetic Approach: Synthesis of Pleurocin A/Matsutakone and Pleurocin B.
Translation of a Polar Biogenesis Proposal into a Radical Synthetic Approach: Synthesis of Pleurocin A/Matsutakone and Pleurocin B.
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DOI：
10.1021/jacs.8b13356
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发表时间：
2019-01
影响因子：
15
通讯作者：
R. Heinze;P. Heretsch
中科院分区：
文献类型：
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作者：
R. Heinze;P. Heretsch
通过重新考虑最初提出的生物起源的极性转变，发展了一种合成最近报道的结构独特的11（9→7）种非甾体化合物pleurocin A/matsutakone（1）和pleurocin B（2）的方法。使用后期中间体的复杂的自由基环化，然后进行氧化淬灭，并锻造了abeo-骨架，而9，11-断-基序是通过使用Treibs型的无汞去饱和将麦角甾醇转化为9，11-断烯醇醚而获得的，氧化键断裂，其预示着醛与烯酮的二氧杂-[4+2]-环加成和结合的转缩醛化/消除，随后是离子氢化。
A synthetic approach to recently reported and structurally unique 11(9→7) abeo-steroids pleurocin A/matsutakone (1) and pleurocin B (2) was developed by reconsidering the originally suggested polar transformations of their biogenesis. An intricate radical cyclization of a late stage intermediate followed by an oxidative quench was used instead and forged the abeo-framework, while the 9,11-seco-motif was obtained by conversion of ergosterol into a 9,11-secoenol ether employing a mercury-free desaturation of the Treibs type, an oxidative bond scission preluding a dioxa-[4+2]-cycloaddition of an aldehyde to an enone and a combined transacetalization/elimination followed by an ionic hydrogenation.