4-<(6-deoxy-2,4-O,O-bis<(1,1-dimethylethyl)dimethylsilyl>-3-O-methyl-α-L-mannopyranosyl)oxy>-5-iodo-2,3-dimethoxy-6-methylbenzoic acid | 138812-91-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-<(6-deoxy-2,4-O,O-bis<(1,1-dimethylethyl)dimethylsilyl>-3-O-methyl-α-L-mannopyranosyl)oxy>-5-iodo-2,3-dimethoxy-6-methylbenzoic acid
• CAS: 138812-91-6
• 化学式: C₂₉H₅₁IO₉Si₂
• 分子量: 726.794
• InChiKey: GPONRENDUZHELE-ZSHCDGJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.23
• 重原子数：
  41.0
• 可旋转键数：
  10.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  101.91
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  4-<(6-deoxy-2,4-O,O-bis<(1,1-dimethylethyl)dimethylsilyl>-3-O-methyl-α-L-mannopyranosyl)oxy>-5-iodo-2,3-dimethoxy-6-methylbenzoic acid 在 4-二甲氨基吡啶 、 草酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 2,4,6-trideoxy-1-O-<<2-(trimethylsilyl)ethyl>amino>-3-O-<(1,1-dimethylethyl)dimethylsilyl>-4-β-D-ribo-hexopyranosyl 4-<(6-deoxy-2,4-O,O-bis<(1,1-dimethylethyl)dimethylsilyl>-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：

  Acetic acid (2R,3R,4S,5S,6S)-5-(tert-butyl-dimethyl-silanyloxy)-2-(2,4-diiodo-5,6-dimethoxy-3-methyl-phenoxy)-4-methoxy-6-methyl-tetrahydro-pyran-3-yl ester 在 吡啶 、 4-二甲氨基吡啶 、 palladium diacetate 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 1,3-双(二苯基膦)丙烷 、 sodium methylate 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 环己烷 、 二甲基亚砜 、 正丁醇 为溶剂， -78.0~65.0 ℃ 、101.33 kPa 条件下， 反应 68.83h， 生成 4-<(6-deoxy-2,4-O,O-bis<(1,1-dimethylethyl)dimethylsilyl>-3-O-methyl-α-L-mannopyranosyl)oxy>-5-iodo-2,3-dimethoxy-6-methylbenzoic acid
  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

文献信息

• Reductive desilanolation as a route to benzonitriles. An application to a concise synthesis of the aromatic sector of calicheamicin
  作者：Steven H. Olson、Samuel J. Danishefsky

  DOI：10.1016/0040-4039(94)80006-5

  日期：1994.10

  The TMS-cyanohydrins of quinones undergo reductive desilanolation in the presence of samarium iodide to form hydroxybenzonitriles. Benzoquinone 1 was converted to the hexasubstituted aromatic fragment of calicheamicin 4 by this method.

  醌的TMS-氰醇在碘化sa的存在下进行还原性脱硅醇化反应，形成羟基苄腈。通过该方法将苯醌1转化为加利车霉素4的六取代的芳族片段。
• Halcomb, Randall L.; Boyer, Serge H.; Danishefsky, Samuel J., Angewandte Chemie, 1992, vol. 104, # 3, p. 314 - 317
  作者：Halcomb, Randall L.、Boyer, Serge H.、Danishefsky, Samuel J.

  DOI：——

  日期：——