62 ティリバリンの立体選択的全合成

概要

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Recently, we have found that aromatic and heteroaromatic organometallics can be aminated efficiently by sequential treatment with diphenyl phosphorazidate (DPPA) and sodium bis(2-methoxyethoxy)-aluminum hydride in a one-pot process. Using the new amination method, we have now succeeded a highly efficient stereoselective convergent synthesis of tilivalline (1) as follows. The oxazoline (10) was aminated by the above method to give the aminooxazoline (11), which was hydrolyzed with hydriodic acid in the presence of red phosphorus, giving m-hydroxyanthranilic acid (25). Condensation of (25) with L-prolinal dimethylacetal hydrochloride (22), derived from Boc-L-proline (20), by the diethyl phosphorocyanidate method afforded the amide (26). Successive treatment of (26) with 1) chlorotrimethylsilane / sodium iodide / pyridine, 2) indole, and 3) zinc chloride in a one-pot process gave tilivalline (1) in excellent yield.
天然有機化合物討論会の論文
1986-09-09