1985 年 33 巻 12 号 p. 5316-5327
New syntheses of the ipecac and Alangium alkaloids possessing the 9, 10-dimethoxy- and 8-hydroxy-9, 10-dimethoxybenzo [a] quinolizidine skeletons (types 1 and 2) have now become possible through generally applicable routes starting from 3-acetylpyridine (5). The routes involve the mercuric acetate-edetic acid oxidation of the 3-acetylpiperidine derivatives 9a, b or the alkaline ferricyanide oxidation of the quaternary salts (26a, b and 27a, b) of 3-acetylpyridine equivalents, Wolff-Kishner reduction of the acetyl group or reductive desulfurization of the thioketal group, sulfenylation-dehydrosulfenylation of the lactams 12a, b, Michael reaction of the α, β-unsaturated lactams 15a, b, and de-ethoxycarbonylation of the Michael adducts 16a, b as the main operations.