ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-(triisopropylsilyl)-β-D-glucopyranoside | 935657-40-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-(triisopropylsilyl)-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-6-ethylsulfanyl-3,4,5-tris[tri(propan-2-yl)silyloxy]oxan-2-yl]methyl 2,2-dimethylpropanoate
• CAS: 935657-40-2
• 化学式: C₄₀H₈₄O₆SSi₃
• 分子量: 777.426
• InChiKey: RLPGTCOYEHOPCC-HRTJLHCRSA-N

物化性质

• 沸点：
  657.8±55.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.74
• 重原子数：
  50
• 可旋转键数：
  21
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-(triisopropylsilyl)-β-D-glucopyranoside 在 吡啶 、 二异丁基氢化铝 、 三氟甲烷磺酸甲酯 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 16.0h， 生成 1,6-bis-O-(3,5-di-O-acetyl-4-O-benzylgalloyl)-2,3,4-tris-O-triisopropylsilyl-β-D-glucopyranose
  参考文献：
  名称：

  Total Synthesis of (+)-Davidiin

  摘要：

  DOI：

  10.1002/anie.201203305
• 作为产物：
  描述：

  ethyl 1-thio-β-D-glucopyranoside 在 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 42.0h， 生成 ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-(triisopropylsilyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Highly β-Selective O-Glucosidation Due to the Restricted Twist-Boat Conformation

  摘要：

  [GRAPHICS]Ethyl 1-thio-2,3,4,6-tetrakis-O-triisopropylsilyl-beta-D-glucopyranoside, ethyl 6-O-benzyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-D-glucopyranoside, and ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-D-glucopyranoside induced highly beta-selective O-glucosidations. Among them, the 6-O-pivaloylated substrate provided the best selectivity up to alpha/beta = 3:97 with cyclohexylmethanol, and the substrate was used for glucosidations with secondary and tertiary alcohols in a highly beta-selective manner. The selectivity would be caused by the twist-boat conformation of the pyranose; this is the first beta-selective O-glucosidation based on conformational control of the pyranose ring.

  DOI：

  10.1021/ol070427b

文献信息

• Highly β-Selective O-Glucosidation Due to the Restricted Twist-Boat Conformation
  作者：Yasunori Okada、Tatsuya Mukae、Kotaro Okajima、Miyoko Taira、Mari Fujita、Hidetoshi Yamada

  DOI：10.1021/ol070427b

  日期：2007.4.1

  [GRAPHICS]Ethyl 1-thio-2,3,4,6-tetrakis-O-triisopropylsilyl-beta-D-glucopyranoside, ethyl 6-O-benzyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-D-glucopyranoside, and ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-D-glucopyranoside induced highly beta-selective O-glucosidations. Among them, the 6-O-pivaloylated substrate provided the best selectivity up to alpha/beta = 3:97 with cyclohexylmethanol, and the substrate was used for glucosidations with secondary and tertiary alcohols in a highly beta-selective manner. The selectivity would be caused by the twist-boat conformation of the pyranose; this is the first beta-selective O-glucosidation based on conformational control of the pyranose ring.
• Total Synthesis of (+)-Davidiin
  作者：Yusuke Kasai、Naoki Michihata、Hidehisa Nishimura、Tsukasa Hirokane、Hidetoshi Yamada

  DOI：10.1002/anie.201203305

  日期：2012.8.6