Synthesis and Characterization of a NovelDiels-AlderAdduct of Codeine
| Autor: | Andrew Coop, Angela Wilks, Alexander D. MacKerell, Kellie Hom, Chayan Acharya, Christopher W. Cunningham |
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| Rok vydání: | 2010 |
| Předmět: |
Steric effects
Diene Stereochemistry Organic Chemistry Codeinone Cleavage (embryo) Biochemistry Article Catalysis Transition state Adduct Inorganic Chemistry chemistry.chemical_compound chemistry Drug Discovery medicine Reactivity (chemistry) Physical and Theoretical Chemistry medicine.drug Diels–Alder reaction |
| Zdroj: | Helvetica Chimica Acta. 93:220-226 |
| ISSN: | 1522-2675 0018-019X |
| DOI: | 10.1002/hlca.200900234 |
| Popis: | The Diels – Alder reaction was applied to 4,5-epoxymorphinan opioids to generate a novel aromatic cycloadduct at C(7) – C(8): Thermolytic cleavage of sultine 8 produced the reactive diene o-quinodimethane 7 which condensed favorably with codeine (11), but not with codeinone (9) or 14- hydroxycodeinone (10), producing the desired tetrahydronaphtho adduct 12 with (7R,8R) geometry (Scheme). The configuration of the cycloadduct was determined by 1D- and 2D-NMR experiments. The unanticipated reactivity of these codeine derivatives was investigated by quantum-mechanical calculations, and it was determined that steric effects of the 6-keto and 14-hydroxy group likely precluded condensation by raising the molecular energy of their respective transition states. |
| Databáze: | OpenAIRE |
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