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通过有机催化 Diels-Alder 反应高对映选择性地获得大麻素型三环化合物。

Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels-Alder reactions.

机构信息

Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry, Fritz-Haber-Weg 6, D-76131 Karlsruhe; Tel: (+49) 721 608-48581 ; Institute of Toxicology and Genetics, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany.

出版信息

Beilstein J Org Chem. 2012;8:1385-92. doi: 10.3762/bjoc.8.160. Epub 2012 Aug 28.

DOI:10.3762/bjoc.8.160
PMID:23019475
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3458765/
Abstract

After prosperous domino reactions towards benzopyrans, the products were used as the starting material in Lewis acid catalyzed and organocatalytic Diels-Alder reactions to build up a tricyclic system. Herein, an asymmetric induction up to 96% enantiomeric excess was obtained by the use of imidazolidinone catalysts. This approach can be utilized to construct the tricyclic system in numerous natural products, in particular the scaffold of tetrahydrocannabinol (THC) being the most representative one. Compared with other published methods, condensation with a preexisting cyclohexane moiety in the precursor is needed to gain the heterogenic tricycle systems, whereas we present a novel strategy towards cannabinoid derivatives based on a flexible modular synthesis.

摘要

苯并吡喃经历了一系列繁荣的多米诺反应之后，产物可以作为起始原料，在路易斯酸催化和有机催化的狄尔斯-阿尔德反应中构建三环体系。在此过程中，通过使用咪唑烷酮催化剂，可以获得高达 96%对映体过量的不对称诱导。这种方法可以用于构建许多天然产物中的三环体系，特别是四氢大麻酚（THC）的支架是最具代表性的一个。与其他已发表的方法相比，需要在前体中与预先存在的环己烷部分缩合来获得杂环的三环体系，而我们提出了一种基于灵活模块化合成的新型大麻素衍生物策略。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/e6cae11b7c4f/Beilstein_J_Org_Chem-08-1385-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/420872023b41/Beilstein_J_Org_Chem-08-1385-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/8e5cc9b57ae5/Beilstein_J_Org_Chem-08-1385-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/eead742d72d1/Beilstein_J_Org_Chem-08-1385-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/cc7bb23fbef0/Beilstein_J_Org_Chem-08-1385-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/07b105bc9160/Beilstein_J_Org_Chem-08-1385-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/42757980fcc1/Beilstein_J_Org_Chem-08-1385-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/2ccd8090a1b2/Beilstein_J_Org_Chem-08-1385-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/ee053c263c58/Beilstein_J_Org_Chem-08-1385-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/27b65bc1574a/Beilstein_J_Org_Chem-08-1385-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/e6cae11b7c4f/Beilstein_J_Org_Chem-08-1385-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/420872023b41/Beilstein_J_Org_Chem-08-1385-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/8e5cc9b57ae5/Beilstein_J_Org_Chem-08-1385-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/eead742d72d1/Beilstein_J_Org_Chem-08-1385-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/cc7bb23fbef0/Beilstein_J_Org_Chem-08-1385-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/07b105bc9160/Beilstein_J_Org_Chem-08-1385-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/42757980fcc1/Beilstein_J_Org_Chem-08-1385-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/2ccd8090a1b2/Beilstein_J_Org_Chem-08-1385-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/ee053c263c58/Beilstein_J_Org_Chem-08-1385-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/27b65bc1574a/Beilstein_J_Org_Chem-08-1385-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e074/3458765/e6cae11b7c4f/Beilstein_J_Org_Chem-08-1385-g011.jpg

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