Reaction of organoaluminium reagents with cyclopropylmethyl acetates and 2-vinylcyclopropane-1,1-dicarboxylate esters.
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概要
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Ring-opening alkylation of cyclopropylmethyl acetates was studied. The acetoxyl group of 7-(1-acetoxyheptyl)norcarane is substituted by the alkyl group upon treatment with trialkylaluminium, but alkylation of <I>trans</I>-1-(1-acetoxyethyl)-2-phenylcyclopropane with trialkylaluminium gives rise to <I>trans</I>-5-phenyl-2-alkenes. The reaction of (1<I>S</I>,2<I>S</I>)-2-phenylcyclopropylmethyl acetate with trimethylaluminium resulted in the complete loss of optical activity to give racemic 4-phenyl-1-pentene. Alkylation of <I>trans</I>-1-(1-acetoxy-3-phenylpropyl)-2-vinylcyclopropane with trialkylaluminium proceeds under regioselective ring-opening to give 3-alkylated <I>trans</I>-8-phenyl-1,5-octadiene (selectivity 73–83%). The regio- and stereochemistry of homoconjugate addition to activated vinylcyclopropanes having a doubly carbonyl substituted ring carbon was studied. Trialkylaluminium on addition to diethyl 2-vinylcyclopropane-1,1-dicarboxylate in a 1,5-manner afford diethyl (2-alkyl-3-butenyl)propanedioate (over 96% selectivity). In contrast, the reaction of this cyclopropane with tetraalkylaluminiumlithium takes place in a 1,7-manner to give diethyl (<I>trans</I>-4-alkyl-2-butenyl)propanedioate with 88–92% selectivity. Clean regiocontrol of the reaction is observed in the methylation of ethyl <I>exo</I>-6-(<I>trans</I>-1-propenyl)-2-oxobicyclo[3.1.0]hexane-1-carboxylate with trimethylaluminium or tetramethylaluminiumlithium. Alkylation with trimethylaluminium proceeds with 86% inversion of the configuration at C(6) of the substrate, affording (2<I>R</I><SUP>*</SUP>,3<I>R</I><SUP>*</SUP>)-2-ethoxycarbonyl-3-[(<I>S</I><SUP>*</SUP>)-<I>trans</I>-1-methyl-2-butenyl]cyclopentanone which is transformed into neonepetalactone.
- 公益社団法人 日本化学会の論文
著者
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YAMAMOTO Hajime
Department of Applied Physics and Chemistry, The University of Electro-Communications
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Hiyama Tamejiro
Department Of Marerial Chemistry Graduate School Of Engineering Kyoto University
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Nozaki Hitosi
Department of Industrial Chemistry, Faculty of Engineering Kyoto University
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Yamamoto Hajime
Department of Industrial Chemistry, Kyoto University
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Morizawa Yoshitomi
Department of Industrial Chemistry, Kyoto University
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Morizawa Yoshitomi
Department of Industrial Chemistry, Faculty of Engineering Kyoto University
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Hiyama Tamejiro
Department of Industrial Chemistry, Faculty of Engineering, Kyoto University
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