YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
インドールアルカロイド類の転換反応(第2報)インドールアルカロイドのC/D環開環ならびに閉環反応とVobasine型アルカロイドの合成について
坂井 進一郎久保 陽徳片野 清昭新間 信夫笹子 久美子
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1973 年 93 巻 9 号 p. 1165-1182

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From the cyanogen bromide reaction of yohimbine (I) in ethanol-chloroform, 3R-ethoxy-3, 4-seco-cyanamide (II) had been obtained by Albright and Goldmann, 6 but it was found that the ratio of reaction products (R and S) depends on the molar ratio of ethanol to the substrate (Table I). Stereospecific ring closing reaction of IIIa and IIIb with hot acetic acid was found to yield I(=IVa) and pseudoyohimbine (IVb), respectively. A similar result was obtained for hirsutine (VI), which gave 3R- and 3S-ethoxy-3, 4-seco-cyanamide (VIIa and b). Both compounds underwent stereospecific ring closure to dihydrocorynantheine (VIIIa) and VI (=VIIIb), respectively. Treatment of gardnerine (XII) with BrCN resulted in the formation of its cyanamide ether (XIII). In the ring closing reaction with hot acetic acid, XIII gave a new iminoindolenine derivative (XIV). Two convenient routes are described for the syntheses of vobasine-type alkaloids from gardnerine acetate (XXVI). When phenyl chloroformate was used instead of BrCN, in a two-phase reaction with aqueous alkali and pure chloroform, Na-methylgardnerine acetate (XXVII) directly provided an amorphous 3-hydroxy-3, 4-seco-urethane derivative (XXVIII) in 60-70% yield. XXVIII was converted to the desired 2-acylindole alkaloid (XXIX), mp 197 -199°, in two steps. Treatment of XXVI with BrCN in 10% methanolpure chloroform resulted in the formation of 3-methoxy-3, 4-seco-cyanamide (XXXIV). Oxidation of XXXIV with t-BuOCl gave 3-keto-3, 4-seco-cyanamide (XXXV) in 39% yield. XXXV was converted to the desired 2-acylindole alkaloid (XXXIX), mp 206.5-209°, in two steps.

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