A convenient synthesis of ethyl 3-(2,2-dihaloethenyl)-2,2-dimethylcyclopropanecarboxylates and its modifications for cis-isomer enrichment.
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概要
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A synthesis of the title compounds <B>5</B> involves the reaction between 3-methyl-2-buten-1-ol and triethyl orthoacetate to produce ethyl 3,3-dimethyl-4-pentenoate, which is followed by the addition of various carbon tetrahalides to the double bond. The reaction of resulting adducts with a base affords <B>5</B> in high yields. Stereoselective preparation of the cis-isomer was achieved by the following two methods: First one involves selective transformation of ethyl 4-bromo-6,6,6-trichloro-3,3-dimethylhexanoate to ethyl 6,6,6-trichloro-3,3-dimethyl-4-hexenoate (<B>8a</B>) with piperidine followed by the selective conversion of <B>8a</B> to <I>cis</I>-2,2-dichloroethenyl compound (<I>cis</I>-<B>5a</B>). Second one is based on the stereoselective cyclization of ethyl 4,6,6,6-tetrachloro-3,3-dimethylhexanoate (<I>t</I>-BuONa/solvent/HMPA) to ethyl <I>cis</I>-2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate which is transformed into <I>cis</I>-<B>5a</B> without cis-trans isomerization.
- 公益社団法人 日本化学会の論文
著者
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KONDO Kiyosi
Sagami Chemical Research Center
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Fujimoto Tamotsu
Sagami Chemical Research Center
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Matsui Kiyohide
Sagami Chemical Research Center
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Takashima Toshiyuki
Sagami Chemical Research Center
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Sugimoto Kikuo
Sagami Chemical Research Center
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Negishi Akira
Sagami Chemical Research Center
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Takahatake Yuriko
Sagami Chemical Research Center
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