Steric effect in regioselective cyclization of 3,4-epoxy alcohols to oxetanes.
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概要
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A number of 3,4-epoxy alcohols, involving critical structural factors for oxetane formation by intramolecular cyclization, were prepared and treated with base under aqueous (KOH in 75% aq DMSO) and anhydrous conditions (NaH in THF). The result of the reactions of <I>cis</I>- and <I>trans</I>-4,5-epoxy-2-rnethyl-2-undecanols, coupled with that of 1-(2,3-epoxybutyl)- and 1-(2,3-epoxy-3-methylbutyl)-1-cyclohexanols (<B>1a</B> and <B>1b</B>), indicated that the regioselective oxetane formations of 3,4-epoxy alcohols with alkoxide anions are much insensitive to steric hindrance at the attacked oxirane rings, compared with the corresponding reactions with carbanions, while that of 1-(2,3-epoxypropyl)-1-cycloalkanols revealed that the relevant reactions depend on bulkiness of attacking alkoxide anions. Moreover, the result of the reactions of 1-(1,2-epoxycycloalkyl)-2-methyl-2-propanols under the aqueous conditions demonstrated that the oxetane formations are affected seriously by steric hindrance at the attacked oxirane rings, although the result was in striking contrast with the corresponding result with carbanions. On the other hand, the reactions of 3,4-epoxy alcohols under the anhydrous conditions proceeded in different manner, depending on the structures of the epoxides; namely, fragmentation took place as major reactions with some epoxides, while intramolecular cyclization occurred predominantly with other epoxides.
- 公益社団法人 日本化学会の論文
著者
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Murai Akio
Department Of Chemistry Faculty Of Science Hokkaido University
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Masamune Tadashi
Department Of Chemistry Faculty Of Science Hokkaido University
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SATO Shingo
Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology
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Ono Mitsunori
Department of Chemistry, Faculty of Science, Hokkaido University
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Abiko Atsushi
Department of Chemistry, Faculty of Science, Hokkaido University
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Sato Shingo
Department of Chemistry, Faculty of Science, Hokkaido University
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