Pi-facial diastereoselection in [4+2]-cycloadditions of 3,4-epoxy-2-methyleneoxolanes with oxadienes : a short synthesis of spiroketals

التفاصيل البيبلوغرافية
العنوان: Pi-facial diastereoselection in [4+2]-cycloadditions of 3,4-epoxy-2-methyleneoxolanes with oxadienes : a short synthesis of spiroketals
المؤلفون: Josselin Chuche, Pierre-Alain Carrupt, Patrick Pale, J. Bouquant, Pierre Vogel
المصدر: Tetrahedron, Vol. 50, No 27 (1994) pp. 8035-8052
سنة النشر: 1994
مصطلحات موضوعية: enol ethers, Allylic rearrangement, chemical-reactivity, Double bond, Stereochemistry, Alder cyclo-additions, Substituent, Epoxide, stereoselectivity, Biochemistry, chemistry.chemical_compound, Drug Discovery, Crotonaldehyde, chemistry.chemical_classification, occurring terpene derivatives, ddc:615, Organic Chemistry, allylic substituents, transition, modeling, structures, Cycloaddition, organic-reactions, chemistry, Enol ether, macrolide total synthesis, Isomerization, diels-alder
الوصف: Hetero Diels-Alder reaction of oxadienes with 3,4-epoxy-2-methyleneoxolanes gave the corresponding 3,4-epoxy-1,6-dioxaspiro[4,5]-dec-7-enes with high stereoselectivity. Good yields of adducts were obtained in the presence of mild Lewis acis, such as zinc or stannous chloride. The spiroketal adducts have been transformed chemio- and stereospecifically by either hydrogenation, hydride reduction or acid catalyzed isomerization. The stereochemical outcome of the cycloadditions has been investigated. The spiroketal adducts always result from an oxadiene addition anti relative to the allylic epoxy substituent. When the oxadiene is substituted suitably as in crotonaldehyde, we demonstrated that the cycloaddition is totally endo selective relative to the enol ether function. Ab initio calculations suggested that 3,4-epoxy-2-methyleneoxolane and 3,4-epoxy-3-methyl-2-methyleneoxolane adopt envelopw conformations with the oxygen atom of the oxolane moiety pointing toward the epoxide ring. No significant distortion from planarity was calculated for the exocyclic double bond of these dienophiles.
اللغة: English
تدمد: 0040-4020
URL الوصول: https://explore.openaire.eu/search/publication?articleId=doi_dedup___::f3444cad8377b1a79c48fea8b4f391e6
https://archive-ouverte.unige.ch/unige:9957
Rights: OPEN
رقم الانضمام: edsair.doi.dedup.....f3444cad8377b1a79c48fea8b4f391e6
قاعدة البيانات: OpenAIRE