Synthesis of (−)-Morphine: Application of Sequential Claisen/Claisen Rearrangement of an Allylic Vicinal Diol
| Autor: | Ryosuke Saito, Shohei Miwa, Hiroki Tanimoto, Takaaki Sato, Noritaka Chida, Masato Ichiki |
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| Rok vydání: | 2012 |
| Předmět: |
chemistry.chemical_classification
Allylic rearrangement Molecular Structure Morphine Double bond Propanols Stereochemistry Organic Chemistry Diol Total synthesis Stereoisomerism General Chemistry Sigmatropic reaction Catalysis Allyl Compounds Claisen rearrangement chemistry.chemical_compound chemistry Alcohols Stereoselectivity Vicinal |
| Zdroj: | Chemistry - A European Journal. 19:264-269 |
| ISSN: | 0947-6539 |
| DOI: | 10.1002/chem.201203284 |
| Popis: | A detailed exploration of the synthesis of (-)-morphine based on sequential [3,3]-sigmatropic rearrangements is described. The sequential Claisen/Claisen rearrangements of an allylic vicinal diol resulted in the stereoselective formation of the two contiguous carbon centers, including a sterically encumbered quaternary carbon, in a single operation. The two ethyl esters generated in this reaction were successfully differentiated during a subsequent Friedel-Crafts-type cyclization. The (-)-morphine double bond was introduced at a late stage in our first-generation synthesis, but was formed at an earlier stage in the second-generation synthesis, resulting in a more efficient route to the end product. |
| Databáze: | OpenAIRE |
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