Synthesis and properties of bridgehead-substituted bicyclo(n.2.2) bridgehead alkenes.
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概要
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The bridgehead-substituted bicyclo[<I>n</I>.2.2] bridgehead alkenes (<B>1b</B>–<B>3b</B>) (<B>1</B>, <I>n</I>=4; <B>2</B>, <I>n</I>=5; <B>3</B>, <I>n</I>=6; <B>b</B>, R=OAc) were synthesized based on the oxidative decarboxylation of [<I>n</I>.2.2]propellanecarboxylic acids with lead tetraacetate. The parent alkene (<B>1a</B>–<B>3a</B>) (<B>a</B>, R=H) and other bridgehead-substituted derivatives (<B>1c</B>–<B>3c</B> and <B>1d</B>–<B>3d</B>) (<B>c</B>, R=OH; <B>d</B>, R=Cl) were prepared from <B>1b</B>–<B>3b</B>. The examination of the <SUP>13</SUP>C NMR chemical shifts of <B>1a</B>–<B>c</B>, <B>2a</B>–<B>c</B>, and <B>3a</B>–<B>c</B> indicates the presence of electronic interaction between the bridgehead double bond (C<SUB>γ</SUB>) and the opposite bridgehead carbon (C<SUB>α</SUB>), being the homoallylic position of the double bond. From the product study and the kinetic results of the solvolysis of the bridgehead chlorides <B>1d</B>–<B>3d</B>, it is indicated that the homoallylic participation of the strained bridgehead double bond to the carbonium ion center located at the opposite bridgehead position operates in the solvolysis of <B>1d</B> and <B>2d</B>. It may be, therefore, concluded that highly strained bridgehead alkenes, especially, bicyclo[4.2.2]decene system, show remarkable homoallylic type α, γ-interaction both in the ground state and in the transition state (carbonium ion).
- 公益社団法人 日本化学会の論文
著者
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Tobe Yoshito
Department Of Applied Fine Chemistry Faculty Of Engineering Osaka University
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Ohtani Masaru
Department Of Frontier Sciences The University Of Tokyo
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Odaira Yoshinobu
Department Of Applied Fine Chemistry Faculty Of Engineering Osaka University
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Sakai Yasuo
Department Of Oral And Maxillofacial Surgery The Nippon Dental University School Of Dentistry At Tok
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Matsumoto Masaharu
Department Of Energy Sciences Tokyo Institute Of Technology
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Ohtani Masaru
Department of Petroleum Chemistry, Faculty of Engineering, Osaka University
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Toyotani Shingo
Department of Petroleum Chemistry, Faculty of Engineering, Osaka University
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Sakai Yasuo
Department of Petroleum Chemistry, Faculty of Engineering, Osaka University
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Matsumoto Masaharu
Department of Petroleum Chemistry, Faculty of Engineering, Osaka University
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