Selective Formation of a Trisubstituted Alkene Motif by trans-Hydrostannation/Stille Coupling: Application to the Total Synthesis and Late-Stage Modification of 5,6-Dihydrocineromycin B
| Autor: | Stephan M. Rummelt, Heiko Sommer, Johannes Preindl, Alois Fürstner |
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| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
Models Molecular Biological Products Stereochemistry Alkene Total synthesis General Chemistry General Medicine Chemistry Techniques Synthetic Alkenes Catalysis Streptomyces Stille reaction Polyketide Lactones chemistry Alkyne metathesis Salt metathesis reaction Motif (music) Selectivity |
| Zdroj: | Angewandte Chemie (International ed. in English). 54(21) |
| ISSN: | 1521-3773 |
| Popis: | Countless natural products of polyketide origin have an E-configured 2-methyl-but-2-en-1-ol substructure. An unconventional entry into this important motif was developed as part of a concise total synthesis of 5,6-dihydrocineromycin B. The choice of this particular target was inspired by a recent study, which suggested that the cineromycin family of antibiotics might have overlooked lead qualities, although our biodata do not necessarily support this view. The new approach consists of a sequence of alkyne metathesis followed by a hydroxy-directed trans-hydrostannation and a largely unprecedented methyl-Stille coupling. The excellent yield and remarkable selectivity with which the signature trisubstituted alkene site of the target was procured is noteworthy considering the rather poor outcome of a classical ring-closing metathesis reaction. Moreover, the unorthodox ruthenium-catalyzed trans-hydrostannation is shown to be a versatile handle for diversity-oriented synthesis. |
| Databáze: | OpenAIRE |
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