Regio-and Stereoselective Terminal Allylic Carboxymethylation of gem-Dimethyl Olefins. Synthesis of Biologically Important Linear Degraded Terpenoids
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概要
- 論文の詳細を見る
gem-Dimethyl olefins (III) were transformed regiospecifically to the terminal β-methallyl sulfides (IV) bearing the methoxycarbonylmethyl substituent on the sulfur atom via (A) methoxycarbonylmethanesulfenyl chloride addition followed by dehydrochlorination or (B) allylic chlorination with SO_2Cl_2 followed by sulfenylation with methyl thioglycolate. Treatment of the sulfides (IV) with tert-BuOK or NaH in N, N-dimethylformamide or dimethyl sulfoxide at room temperature gave stereoselectively the sulfur-free esters (V) through a novel one-pot desulfurizative [2,3]-sigmatropic rearrangement. By utilizing this method, biologically and pharmacologically important linear degraded terpenoids, a diol component (1) of the pheromonal secretion of the queen butterfly and several ω-quinoid acids (4,n=1,2) and (5,n=1,2), which are metabolites of polyisoprenoidquinones, were synthesized.
- 公益社団法人日本薬学会の論文
- 1985-05-25
著者
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正木 幸雄
Gifu Pharmaceutical University
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正木 幸雄
岐阜薬科大学:(現)名城大学薬学部薬化学教室
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鍛冶 健司
Gifu Pharmaceutical University
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佐久間 和彦
Gifu College of Pharmacy
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鍛冶 健司
Gifu College Of Pharmacy
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