A concise synthesis of berkelic acid inspired by combining the natural products spicifernin and pulvilloric acid.
A concise synthesis of berkelic acid inspired by combining the natural products spicifernin and pulvilloric acid.
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结合天然产物香料素和普维洛酸，得到了山茱萸酸的简明合成。
DOI：
10.1021/ja905387r
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发表时间：
2009-08-19
影响因子：
15
通讯作者：
De Brabander, Jef K.
中科院分区：
文献类型：
--
作者：
Bender, Christopher F.;Yoshimoto, Francis K.;Paradise, Christopher L.;De Brabander, Jef K.
我们描述了一个简洁的结构新颖的真菌极端微生物代谢产物伯克利酸的合成-一个明确的分配C22立体化学的努力。我们的合成方法的灵感来自于认识到，berkelic酸显示的结构特征，让人想起其他两种真菌代谢产物，spicifernin和pulvilloric酸。基于这一概念，我们进行了一种合成，其特征在于银催化的级联脱芳构化-环异构化-环加成序列以偶联两个天然产物启发的片段。值得注意的是，在七个步骤和三次纯化中制备了具有确定的C22立体化学的spicifernin样合成子（24-28%总产率）。开发了一种潜在有用的反选择性缀合炔丙基化反应以引入邻位立体二联体。另一个偶联伙伴，芳香族前体pulvilloric酸甲酯的对映收敛合成，在八个步骤和48%的总收率。在此基础上，以10步最长的线性反应完成了小檗酸及其C22差向异构体的全合成，总收率为11-27%。
We describe a concise synthesis of the structurally novel fungal extremophile metabolite berkelic acid – an effort leading to an unambiguous assignment of C22 stereochemistry. Our synthetic approach was inspired by the recognition that berkelic acid displays structural characteristics reminiscent of two other fungal metabolites, spicifernin and pulvilloric acid. Based on this notion, we executed a synthesis that features a Ag-catalyzed cascade dearomatization-cycloisomerization-cycloaddition sequence to couple two natural product inspired fragments. Notably, a spicifernin-like synthon was prepared with defined C22 stereochemistry in seven steps and three purifications (24–28% overall yield). A potentially useful anti-selective conjugate propargylation reaction was developed to introduce the vicinal stereodiad. An enantioconvergent synthesis of the other coupling partner, the aromatic precursor to pulvilloric acid methyl ester, was achieved in eight steps and 48% overall yield. The total synthesis of berkelic acid and its C22 epimer was thus completed in 10 steps longest linear sequence and 11–27% overall yield.
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DOI：
10.1039/j39690001068
发表时间：
1969-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC
影响因子：
--
作者：
BARRETT, GC;MCOMIE, JFW;TANENBAUM, SW
通讯作者：
TANENBAUM, SW
影响因子：
--
作者：
Naemura, K;Murata, M;Tobe, Y
通讯作者：
Tobe, Y
影响因子：
2.9
作者：
TANENBAUM, SW;NAKAJIMA, S
通讯作者：
NAKAJIMA, S
影响因子：
5.2
作者：
Liu, Bo;De Brabander, Jef K.
通讯作者：
De Brabander, Jef K.
影响因子：
3.8
作者：
NAKAJIMA, H;HAMASAKI, T;TAKEUCHI, Y
通讯作者：
TAKEUCHI, Y