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螺旋细柄菌素A和B的全合成

Total synthesis of spirotenuipesines A and B.

作者信息

Dai Mingji, Krauss Isaac J, Danishefsky Samuel J

机构信息

Department of Chemistry, Columbia University, Havemeyer Hall, New York, New York 10027, USA.

出版信息

J Org Chem. 2008 Dec 19;73(24):9576-83. doi: 10.1021/jo8016814.

DOI:10.1021/jo8016814
PMID:18973385
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2646666/
Abstract

Spirotenuipesines A and B, isolated from the entomopathogenic fungus Paecilomyces tenuipes by Oshima and co-workers, have been synthesized. The synthesis features the highly stereoselective construction of two vicinal all-carbon quaternary centers (C(5) and C(6)) via an intramolecular cyclopropanation/radical initiated fragmentation sequence and a diastereoselective intermolecular Diels-Alder reaction between alpha-methylenelactone dienophile 20 and synergistic diene 6a. Installation of the C(9) tertiary alcohol occurred via nucleophilic methylation. An RCM reaction to produce a tetrasubstituted double bond in the presence of free allylic alcohol and homoallylic oxygenated functional group is also described. This route shortened the synthesis of 11 from 9 steps to 3 steps. We have further developed a strategy to gain access to optically active spirotenuipesines A and B through the synthesis of enantioenriched 10 from commercially available R-(-)-epichlorohydrin.

摘要

大岛及其同事从昆虫病原真菌细脚拟青霉中分离出的螺旋细脚菌素A和B已被合成。该合成的特点是通过分子内环丙烷化/自由基引发的碎片化序列以及α-亚甲基内酯亲双烯体20与协同双烯6a之间的非对映选择性分子间狄尔斯-阿尔德反应，高度立体选择性地构建了两个相邻的全碳季碳中心（C(5)和C(6)）。C(9)叔醇的引入是通过亲核甲基化实现的。还描述了在游离烯丙醇和高烯丙基氧化官能团存在下通过RCM反应生成四取代双键的过程。该路线将11的合成步骤从9步缩短至3步。我们进一步开发了一种策略，通过从市售的R-(-)-环氧氯丙烷合成对映体富集的10来获得光学活性的螺旋细脚菌素A和B。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/d2eb765753d1/jo-2008-016814_0014.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/fb201b11a536/jo-2008-016814_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/143401e9b910/jo-2008-016814_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/83f52218eaec/jo-2008-016814_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/2deb00aa6b4f/jo-2008-016814_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/20ba5602ee22/jo-2008-016814_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/f565bce19157/jo-2008-016814_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/75e197c1dc8e/jo-2008-016814_0013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/d2eb765753d1/jo-2008-016814_0014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/561d1f140c6c/jo-2008-016814_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/87666abb059c/jo-2008-016814_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/f839da494084/jo-2008-016814_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/64c52e951f47/jo-2008-016814_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/6717e079c2c2/jo-2008-016814_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/fb201b11a536/jo-2008-016814_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/143401e9b910/jo-2008-016814_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/83f52218eaec/jo-2008-016814_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/2deb00aa6b4f/jo-2008-016814_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/20ba5602ee22/jo-2008-016814_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/f565bce19157/jo-2008-016814_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/75e197c1dc8e/jo-2008-016814_0013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f4e/2646666/d2eb765753d1/jo-2008-016814_0014.jpg

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