48 糖類の化学変換 : トリアルキルスズ基を用いる水酸基の活性化

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Recently silylated organic molecules have been extensively employed in organic reactions in order to modify the reactivity of original molecules in the field of cabohydrate and nucleoside chemistry. In this report we described mild and specific transformations of carbohydrate based on the reactivity of stannylated compounds. A) Nucleoside synthesis: "Stannyl Hilbert Johnson" Stannylated pyrimidines(IIa-IId) synthesized from corresponding pyrimidines(Ia-Id) very easily, were treated with peracylated sugar (III) in the presence of Friedel-Crafts catalyst to afford corresponding nucleosides(IVa-IVd) stereoselectively in high yield. B) Glycoside synthasus: Reaction of acetobromoglucose(X) with trin-butyltinmethoxide(TBSn methoxide) under mild condition gave methyl β-D-glucoside(XIII, 23%) and 1,6-anhydroglucose der. (XII, 45.5%). Reaction of (X) with TBSn phenoxide(XV) in the presence of catalytic amount of Friedel-Crafts cat. gave phenyl glucoside(XVI, 61%). Reaction of tetrabenzylglucopyranosyl chloride (XVII) was also examined. C) Oxidative transformation: "Oxidative esterification" Oxidation of TBSn alkoxide by NBS in CCl_4 at ambient temperature were examined. Reaction conditions are mild. Tields are high. I)in the absence of added aldehyde: I-i)primary alcohol(RCH_2OH) gave dimeric ester(RCH_2OCOR). I-ii)secondary alcohol(R'R"CHOH) gave ketone(R'R".CO) I-iii)primary alcohol at benzyl or allyl(RCH_2OH) gave aldehyde(RCHO). II)in the presence of added aldehyde(RCHO): II-i)primary alcohol(excluding allyl or benzyl)RCH_2OH gave R'CH_2OCOR II-ii)secondary alcohol(R'R"CHOH) gave ester(R'R"CHOCOR).
1975-10-01

48 糖類の化学変換 : トリアルキルスズ基を用いる水酸基の活性化

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