The first total synthesis of (+/-)-ingenol |
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Authors: | Winkler Jeffrey D Rouse Meagan B Greaney Michael F Harrison Sean J Jeon Yoon T |
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Affiliation: | Department of Chemistry, The University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA. winkler@sas.upenn.edu |
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Abstract: | The first total synthesis of (+/-)-ingenol has been achieved. The key features of the synthesis include the use of a highly diastereoselective Michael reaction to fix the C-11 methyl stereochemistry and the incorporation of the dimethylcyclopropane via diastereoselective carbene addition to the Delta13,14 olefin. The intramolecular dioxenone photoaddition-fragmentation sequence leads to the establishment of the critical C-8/C-10 trans intrabridgehead stereochemistry, a central challenge in the synthesis of ingenanes. The completion of the synthesis proceeds using the C-6alpha hydroxymethyl group as the sole handle for oxidation of seven contiguous carbon centers. |
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