Chemical Transformation of Protoberberines. V. Photochemical Valence Isomerization of Berberinephenolbetaines to 8,14-Cycloberbines, Versatile Aziridine Derivatives for a Novel and Efficient Entry to Spirobenzylisoquinolines and Benzindenoazepines

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概要

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• Irradiation of berberinephenolbetaine (12a) and its 8-alkyl derivatives (12b-e) readily effected valence isomerization to afford the corresponding novel 8,14-cycloberbines (13a-e) in high yields. On treatment with ethyl chloroformate, the 8,14-cycloberbines (13a, 13b, and 13c) were efficiently converted to the spirobenzylisoquinolines (14,15,and 16-18,respectively) via regioselective C_8-N bond cleavage. The 8,14-cycloberbine (13a), on treatment with methyl iodide, provided the benzindenoazepine (21) through regioselective C_<14>-N bond cleavage, whereas 8-methyl- and 8-ethyl-8,14-cycloberbine (13b and 13c) gave 8-methylidene- and (Z)-8-ethylidenespirobenzylisoquinoline (22 and 23), respectively. Irradiation of 8-methoxyberberinephenolbetaine (26) directly afforded the spirobenzylisoquinoline (31) having a ketone and a ketal on the five-membered ring. The product (31) was converted easily to a variety of spirobenzylisoquinolines such as the diketone (36), the hydroxy-ketal (38), and the keto-alcohol derivatives (41 and 42) in excellent yields.

• 社団法人日本薬学会の論文
• 1984-06-25

著者

• 花岡 美代次

  Faculty of Pharmaceutical Sciences, Kanazawa University

• 花岡 美代次

  金沢大学薬学部

• 花岡 美代次

  Faculty Of Pharmaceutical Sciences Osaka University

• 花岡 美代次

  Faculty Of Pharmaceutical Sciences Kanazawa University

• 向 智里

  金沢大学薬学部

• 向 智里

  Faculty of Pharmaceutical Sciences, Kanazawa University

• 安田 信吾

  金沢大・薬

• 詠 和良

  Faculty of Pharmaceutical Sciecnes, Kanazawa University

• 向 智里

  Faculty Of Pharmaceutical Sciences Osaka University

• 詠 和良

  Faculty Of Pharmaceutical Sciecnes Kanazawa University

• 安田 信吾

  Faculty of Pharmaceutical Sciences, Kanazawa University

• 岡嶋 恵子

  Faculty of Pharmaceutical Sciences, Kanazawa University

• 岡嶋 恵子

  Faculty Of Pharmaceutical Sciences Kanazawa University

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