126(P76) Cynanchum hancockianumより単離された二糖グリコシド、neohancoside A,B,Cの合成(ポスター発表の部)
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概要
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Neohancoside A(1), B(2), C(3) are novel monoterpene and phenol diglycosides isolated from Cynanchum hancockianum which is a Chainese folk medicine having antitumor activity. The diglycoside moiety of 1, 2 and 3 is β-D-xylopyranosyl (1→6)-β-D-glucopyranose which is glycosylated by linalool, 9-hydroxylinalool, 2-hydroxyacetophenone, respectively. The first synthesis of 1, 2, 3 were examined to investigate their bioactivities and also to determine the absolute configuration of 1 and 2. Our synthetic strategy toward 1 and 2 consists of the glycosylation reaction of linalool and 9-hydroxylinalool with a glucosyl fluoride 8b using AgClO_4 and zirconocene dichloride folowed by the selective deprotection of 6-O-protective group in the glucose unit, and glycosylating the resulting monoglycoside with a xylosyl bromide using AgOTf and 2,4,6-collidine to give diglycosides. The asymmetry of C-3 in 1 and 2 was introduced efficiently by separating the diastereomers of synthetic intermediates 11 and 13. The absolute configuration of linalool and 9-hydroxylinalool moiety were determined by enzymatic degradation of synthetic intermediates 22 and 23 giving R-(-)-linalool and R-(-)-8-hydroxylinalool, respectively. Strategy of 3 consists of the glycosylation reaction of 2-hydroxyacetophenone with a glucosyl bromide 32 using phase transfer catalyst in aq. NaOH/CH_2Cl_2, then glycosylating the resulting phenol monoglycoside with a xylosyl bromide giving phenol diglycoside. Physicochemical data of our synthetic 1, 2 and 3 were coincedent with the data of natural neohancoside A, B and C, respectively.
- 天然有機化合物討論会の論文
- 1996-09-02
著者
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有馬 志保
北里大薬
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針谷 義弘
北里大薬
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梶 英輔
School Of Pharmaceutical Sciences Kitasato University
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梶 英輔
北里大薬
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根田 八重子
北里大薬
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戸井田 恒之
北里大薬
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武田 収功
北里大理
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