A peculiar transition-metal-free cyclodimerization of propargylic alcohols to vinyl bicyclic ketals

A peculiar transition-metal-free cyclodimerization of propargylic alcohols to vinyl bicyclic ketals

Propargylic alcohols, alkylaryl(hetaryl)ethynyl carbinols, under transition-metal-free conditions (KOH/DMSO, 70–80 °C, 10–15 min) unexpectedly undergo stereoselective cyclodimerization to 7-methylene-6,8-dioxabicyclo[3.2.1]octanes having the scaffold of known insect pheromones and marine toxins. Und...

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Veröffentlicht in:Tetrahedron 2012-01, Vol.68 (4), p.1241-1246
Hauptverfasser: Trofimov, Boris A., Schmidt, Elena Yu, Bidusenko, Ivan A., Ushakov, Igor’ A., Protsuk, Nadezhda I., Zorina, Nadezhda V., Mikhaleva, Albina I.
Format: Artikel
Sprache:eng
Schlagworte:
6,8-Dioxabicyclo[3.2.1]octanes
Acetylene
Acetylenic alcohols
Alcohols
Insects
Marine
Scaffolds
Super base
Tetrahedrons
Toxins
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Zusammenfassung:Propargylic alcohols, alkylaryl(hetaryl)ethynyl carbinols, under transition-metal-free conditions (KOH/DMSO, 70–80 °C, 10–15 min) unexpectedly undergo stereoselective cyclodimerization to 7-methylene-6,8-dioxabicyclo[3.2.1]octanes having the scaffold of known insect pheromones and marine toxins. Under acetylenic pressure the yields of bicyclic ketals reach 80%. In all the cases, the cyclodimers are formed exclusively as one diastereomer. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2011.11.050