2-(trimethylsilyl)ethyl <(2,4,6-trideoxy-3-O-(triethylsilyl)-4-thio-β-D-ribo-hexopyranosyl)oxy>carbamate | 168567-25-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: 2-(trimethylsilyl)ethyl <(2,4,6-trideoxy-3-O-(triethylsilyl)-4-thio-β-D-ribo-hexopyranosyl)oxy>carbamate
• CAS: 168567-25-7
• 化学式: C₁₈H₃₉NO₅SSi₂
• 分子量: 437.748
• InChiKey: AAJNRXONCCGEDM-LTIDMASMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.81
• 重原子数：
  27.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  66.02
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  4-<(6-deoxy-3-O-methyl-2,4-O,O-bis(triethylsilyl)-α-L-mannopyranosyl)oxy>-5-iodo-2,3-dimethoxy-6-methylbenzoic acid chloride 、 2-(trimethylsilyl)ethyl <(2,4,6-trideoxy-3-O-(triethylsilyl)-4-thio-β-D-ribo-hexopyranosyl)oxy>carbamate 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以62%的产率得到2,4,6-trideoxy-1-O-<<2-(tromethylsilyl)ethyl>amino>-3-O-(triethylsilyl)-4-β-D-ribo-hexopyranosyl-4-<(6-deoxy-2,4-O,O-bis(triethylsilyl)-3-O-methyl-α-L-mannopyranosyl)oxy>-5-iodo-2,3-dimethoxy-6-methylthiobenzoate
  参考文献：
  名称：

  Studies Related to the Carbohydrate Sectors of Esperamicin and Calicheamicin: Definition of the Stability Limits of the Esperamicin Domain and Fashioning of a Glycosyl Donor from the Calicheamicin Domain

  摘要：

  The core trisaccharide regions of esperamicin and the aryltetrasaccharide region of calicheamicin have been synthesized. The minimum protection modalities necessary to stabilize structures against rearrangement to an isomeric azafuranose series were ascertained (see compounds 12 and 65). Deprotection of the 2-(trimethylsilyl)ethoxycarbonyl carbamate from 65 led to azafuranose 14 characterized as methyl glycoside 15. Using this insight, it was possible to fashion, for the first time, a pre-glycosyl donor (see compound 128) corresponding to the complete arylsaccharide sector of calicheamicin gamma(1)(I) at the oxidation level of the domain. Among the key assembly strategies were the conversion of alpha-thiophenylpseudoglycals to allal derivatives (see 44 --> 45); the interfacing of epoxide-mediated glycosylation with iodoglycosylation (see 30 --> 47 --> 48); the synthesis of hydroxylamine glycosides via triflate displacement (see 61 + 91 --> 101); and a new route to p-hydroxybenzonitriles (see formation of 86).

  DOI：

  10.1021/ja00126a013
• 作为产物：
  描述：

  (2R,3R,6R)-2-Hydroxymethyl-6-phenylsulfanyl-3,6-dihydro-2H-pyran-3-ol 在 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 四丁基溴化铵 、 三苯基膦氢溴酸盐 、 二正丁基氧化锡 、 potassium carbonate 、 二乙胺 、 三乙胺 、 间氯过氧苯甲酸 、 乙硫醇 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 2-(trimethylsilyl)ethyl <(2,4,6-trideoxy-3-O-(triethylsilyl)-4-thio-β-D-ribo-hexopyranosyl)oxy>carbamate
  参考文献：
  名称：

  Studies Related to the Carbohydrate Sectors of Esperamicin and Calicheamicin: Definition of the Stability Limits of the Esperamicin Domain and Fashioning of a Glycosyl Donor from the Calicheamicin Domain

  摘要：

  The core trisaccharide regions of esperamicin and the aryltetrasaccharide region of calicheamicin have been synthesized. The minimum protection modalities necessary to stabilize structures against rearrangement to an isomeric azafuranose series were ascertained (see compounds 12 and 65). Deprotection of the 2-(trimethylsilyl)ethoxycarbonyl carbamate from 65 led to azafuranose 14 characterized as methyl glycoside 15. Using this insight, it was possible to fashion, for the first time, a pre-glycosyl donor (see compound 128) corresponding to the complete arylsaccharide sector of calicheamicin gamma(1)(I) at the oxidation level of the domain. Among the key assembly strategies were the conversion of alpha-thiophenylpseudoglycals to allal derivatives (see 44 --> 45); the interfacing of epoxide-mediated glycosylation with iodoglycosylation (see 30 --> 47 --> 48); the synthesis of hydroxylamine glycosides via triflate displacement (see 61 + 91 --> 101); and a new route to p-hydroxybenzonitriles (see formation of 86).

  DOI：

  10.1021/ja00126a013