Total Synthesis of the Phenylnaphthacenoid Type II Polyketide Antibiotic Formicamycin H via Regioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer [4 + 2] Cycloaddition,Journal of the American Chemical Society

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Total Synthesis of the Phenylnaphthacenoid Type II Polyketide Antibiotic Formicamycin H via Regioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer [4 + 2] Cycloaddition
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-12 , DOI: 10.1021/jacs.4c09068
Guanyu Hu ₁ , Rosalie S Doerksen ₁ , Brett R Ambler ₁ , Michael J Krische ₁

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The first total synthesis of the pentacyclic phenylnaphthacenoid type II polyketide antibiotic formicamycin H is described. A key feature of the synthesis involves the convergent, regioselective assembly of the tetracyclic core via ruthenium-catalyzed α-ketol-benzocyclobutenone [4 + 2] cycloaddition. Double dehydration of the diol-containing cycloadduct provides an achiral enone, which upon asymmetric nucleophilic epoxidation and further manipulations delivers the penultimate tetracyclic trichloride in enantiomerically enriched form. Subsequent chemo- and atroposelective Suzuki cross-coupling of the tetracyclic trichloride introduces the E-ring to complete the total synthesis. Single-crystal X-ray diffraction analyses of two model compounds suggest that the initially assigned stereochemistry of the axially chiral C6–C7 linkage may require revision.

中文翻译：

通过区域选择性钌催化氢自动转移 [4 + 2] 环加成全合成苯基萘类 II 型聚酮抗生素福米霉素 H

首次全合成五环苯基并四苯类 II 型聚酮化合物抗生素福米霉素 H。该合成的一个关键特征涉及通过钌催化的 α-酮醇-苯并环丁烯酮 [4 + 2] 环加成对四环核进行聚合、区域选择性组装。含二醇的环加合物的双重脱水提供非手性烯酮，其在不对称亲核环氧化和进一步操作后以对映体富集的形式提供倒数第二个四环三氯化物。随后四环三氯化物的化学选择性和肌醇选择性 Suzuki 交叉偶联引入 E 环以完成全合成。两种模型化合物的单晶 X 射线衍射分析表明，最初指定的轴向手性 C6-C7 连接的立体化学可能需要修改。

更新日期：2024-09-12

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