phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-galactopyranoside | 947256-88-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-galactopyranoside
• CAS: 947256-88-4
• 化学式: C₃₇H₆₄O₅SSi₃
• 分子量: 705.235
• InChiKey: LEDIXNGVZKZSJG-YODGASFJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.89
• 重原子数：
  46.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-galactopyranoside 在 三氟甲磺酸 N-碘代丁二酰亚胺 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 phenyl 2,3,4-tri-O-benzyl-4-O-(6-O-benzyl-α-D-galactopyranosyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 phenyl 6-O-benzyl-1-thio-β-D-galactopyranoside 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 24.0h， 以58%的产率得到phenyl 6-O-benzyl-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l