66 セスキテルペンラクトン類の合成研究(V) : Saussurea lactoneおよびArborescinの全合成

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概要

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• I) Saussurea lactone, a typical elemanolide has been synthesized via a novel fragmentation reaction of an epoxymesylate (7). The starting material is an acetal (1) which was prepared from α-santonin. Deacetalization of 1 with boiling 50% AcOH aq gave a β,γ-unsaturated ketone (2). Reduction of 2 with LiAl(t-BuO)_3H and successive treatment with m-chloroperbenzoic acid gave an epoxide (6). Mesylation of 6 afforded epoxymesylate (7). Fragmentation reaction of 7 with Al(i-PrO)_3 in boiling toluene gave an ester (9) which was transformed into a lactone (10). Acetylation of 10 and successive reduction of the resulting acetate (11) with Li in liquid ammonia gave a hemiacetal (12) which was transformed into saussurea lactone by Collins oxidation. II) Arborescin has been synthesized in 11 steps from epoxyacetal (13). Treatment of 13 with Al(i-PrO)_3 in boiling toluene gave allyl alcohol (14). Catalytic hydrogenation of 14 and successive benzoylation gave a benzoate (16). Deacetalization of 16 with 50% AcOH aq gave a ketone (17) which was transformed into a mesylate (20) by reduction with LiAl(t-BuO)_3H and successive mesylation of the resulting β-alcohol (19). Solvolytic rearrangement of 20 gave benzoates (21) and (22). Epoxidation of 22 gave 1β,10β-epoxide (24) and 1α,10α-epoxide (23). Hydrolysis of 24 gave an alcohol (25) which was transformed into arborescin by mesylation and successive treatment of the resulting mesylate with LiBr and Li_2CO_3 in DMF. The same treatment of 23 gave an epoxide (28) and an allyl alcohol(29). From these results the stereochemistry of the epoxide ring of arborescin has been determined to be β-orientation.

• 天然有機化合物討論会の論文
• 1978-08-22

著者

• 安東 政義

  東北大理

• 高瀬 嘉平

  Department of Chemistry, Faculty of Science, Tohoku University

• 安東 政義

  東北大・理

• 高瀬 嘉平

  東北大・理

• 赤羽 厚

  東北大・理

• 田島 潔

  東北大・理

• 高瀬 嘉平

  Department Of Chemistry Faculty Of Science Tohoku University

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