Highly regioselective .ALPHA.-addition of alkynyl and alkenyl Grignard reagents to 1-alkoxycarbonylpyridinium salts and its application to synthesis of 1-azabicycloalkanes and (.+-.)-solenopsin A.

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概要

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• Nucleophilic addition of a variety of alkynyl and alkenyl Grignard reagents to 1-methoxycarbonylpyridinium chloride takes place at the α-position in a highly regioselective manner to give 2-substituted 1-methoxycarbonyl-1,2-dihydropyridines exclusively, while, with alkyl Grignard reagents, a lack of the regioselectivity is observed. These results may be explained by the HSAB principle. The high α-regioselectivity is preserved in the cases of 2-substituted pyridines as well, giving 2,6-disubstituted 1,2-dihydropyridines exclusively, which can be transformed stereoselectively into <I>cis</I>- and <I>trans</I>-2,6-dialkylated piperidines. These highly regioselective α-alkynylations of 1-methoxycarbonylpyridinium salts are exploited in synthesis of 1-azabicycloalkanes as well as (±)-solenopsin A.

• 公益社団法人 日本化学会の論文

著者

• Yamaguchi Ryohei

  Department Of Natural Environment Sciences Faculty Of Integrated Human Studies Kyoto University

• Matsuki Toshitsugu

  Department of Industrial Chemistry, Faculty of Engineering, Kyoto University

• Nakazono Yutaka

  Department of Industrial Chemistry, Faculty of Engineering, Kyoto University

• Hata Ei-ichiro

  Department of Industrial Chemistry, Faculty of Engineering, Kyoto University

• Kawanisi Mituyosi

  Department of Industrial Chemistry, Faculty of Engineering, Kyoto University

• Nakazono Yutaka

  Department of Applied Chemistry, Faculty of Engineering, Doshisha University

• Yamaguchi Ryohei

  Department of Applied Chemistry, Faculty of Engineering, Yokohama National University

• Kawanisi Mituyosi

  Department of Industrial Chemistry, Faculty of Engineering Kyoto University

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