51 AlangiumアルカロイドDemethyltubulosineの構造 : (±)-10-Demethyltubulosineの合成
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The target molecule (±)-VIII was selected for synthesis with a view to establishing the structure of demethyltubulosine, one of the benzoquinolizidine alkaloids isolated from Alangium lamarckii Thw. (family Alangiaceae). Condensation of the tricyclic amino acid X, prepared from ethyl (±)-trans-5-ethyl-2-oxo-4-piperidineacetate in eight steps according to previously reported procedure, with 5-benzyloxytryptamine using the coupling reagent diethyl phosphorocyanidate gave the tryptamide XI (96% yield), which was then cyclized (POCl_3, boiling toluene) to XII in 59% yield. Catalytic hydrogenation of XII (Pt/H_2, dioxane) and chromatographic separation of the products afforded the base XIII (25% yield) and its 1'-epimer (XIV) (54% yield). The two bases were separately debenzylated (Pd-C/H_2, MeOH-AcOH) to produce the corresponding phenolic bases, VIII and XV, in good yields. The relative configuration at C-1' of XIII, XIV, VIII, and XV was confirmed by the method given in the literature. The UV, IR, PMR, and mass spectra and chromatographic behavior of the synthetic (±)-VIII thus obtained were found to be identical with those of natural demethyltubulosine, establishing the structure of this alkaloid as 10-demethyltubulosine.
- 天然有機化合物討論会の論文
- 1980-09-10
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関連論文
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- 51 AlangiumアルカロイドDemethyltubulosineの構造 : (±)-10-Demethyltubulosineの合成