Polyunsaturated C-Glycosidic 4-Hydroxy-2-pyrone Derivatives: Total Synthesis Shows that Putative Orevactaene Is Likely Identical with Epipyrone A
| Autor: | Saskia Schulthoff, Johannes Preindl, Julia B. Lingnau, Cornelia Wirtz, Alois Fürstner |
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| Rok vydání: | 2017 |
| Předmět: |
Glycosylation
Stereochemistry Alkyne 010402 general chemistry 01 natural sciences Catalysis Tungsten chemistry.chemical_compound Cycloisomerization Glycosides Pyrans chemistry.chemical_classification Bicyclic molecule Molecular Structure 010405 organic chemistry Total synthesis Glycosidic bond Stereoisomerism General Medicine General Chemistry Orevactaene 0104 chemical sciences chemistry 2-Pyrone Cyclization Pyrones Gold |
| Zdroj: | Angewandte Chemie (International ed. in English). 56(26) |
| ISSN: | 1521-3773 |
| Popis: | Orevactaene and epipyrone A were previously thought to comprise the same polyunsaturated tail but notably different C-glycosylated 4-hydroxy-2-pyrone head groups. Total synthesis now shows that the signature bicyclic framework assigned to orevactaene is a chimera; the compound is almost certainly identical with epipyrone A, whose previously unknown stereochemistry has also been established during this study. Key to success was the ready formation of the bicyclic core of putative orevactaene by a sequence of two alkyne cycloisomerization reactions using tungsten and gold catalysis. Equally important was the flexibility in the assembly process gained by the use of heterobimetallic polyunsaturated modules whose termini could be selectively and consecutively addressed in a practical one-pot cross-coupling sequence. |
| Databáze: | OpenAIRE |
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