Cyclopropanation of norbornadiene and dicyclopentadiene on catalytic isomerization of the methyl esters of 1-alkylcyclopropene-3-carboxylic acids. A new route to polycyclic compounds of the vinylcyclopropane series
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The ability of methyl esters of 1-alkylcyclopropene-3-carboxylic acids to cyclopropanate norbornadiene or dicyclopentadiene, in the presence of copper (I) chloride or its complexes, with the formation in up to 75% yield of the corresponding vinylcyclopropane adducts has been discovered. Products were the methyl esters of 3-(tricyclo[3. 2.1.02,4]oct-6-en-3-yl)alk-2-enoic and 3-(tetracyclo[5.3.1.02,608,10]undec-3-en-9-yl)alk-2-enoic acids respectively.
The methyl esters of 1-alkylcyclopropenecarboxylic acids were isomerized, in a medium of cycloocta-1,5-diene, cyclohexene, methylenecyclopropane, or methyl acrylate in the presence of copper (I) chloride or its complexes, into 2-methoxy-4-alkylfuran (yields up to 65%) and partially oligomerized, but with cyclopentadiene the corresponding diene adduct was formed.
A concerted mechanism has been proposed and theoretically substantiated for the formation of vinylcyclopropane derivatives from substituted cyclopropenes and olefins in the coordination sphere of copper without the participation of vinylcarbenes or their complexes.
KeywordsCopper Chloride Adduct Methyl Ester Cyclohexene
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