Enantioselective Total Synthesis of Terreumols A and C from the Mushroom Tricholoma terreum
| Autor: | Thomas Lindel, Peter G. Jones, Alex Frichert |
|---|---|
| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
Models Molecular Magnetic Resonance Spectroscopy Double bond biology 010405 organic chemistry Tricholoma terreum Stereochemistry Terpenes Enantioselective synthesis Absolute configuration Total synthesis Stereoisomerism General Chemistry 010402 general chemistry biology.organism_classification Metathesis 01 natural sciences Benzoquinone Catalysis 0104 chemical sciences Ring-closing metathesis chemistry X-Ray Diffraction Agaricales |
| Zdroj: | Angewandte Chemie (International ed. in English). 55(8) |
| ISSN: | 1521-3773 |
| Popis: | The cytotoxic meroterpenoids terreumol A and C from the grey knight mushroom Tricholoma terreum were synthesized for the first time. The key step of the enantioselective total synthesis of terreumol C is a ring-closing metathesis to form a trisubstituted Z double bond embedded in the 10-membered ring of the [8.4.0] bicycle. Interestingly, the presence of a free hydroxy group in the metathesis precursor prevents cyclization and favors cross metathesis. (-)-Terreumol C was converted into (-)-terreumol A by diastereoselective epoxidation. Starting from 2-bromo-3,5-dimethoxybenzaldehyde, 14 steps with an overall yield of 23 % are needed for the synthesis of (-)-terreumol A. X-ray analysis of the benzoquinone analogue of terreumol A provides independent proof of the absolute configuration. |
| Databáze: | OpenAIRE |
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