methyl 4,6-dideoxy-2,3-dibenzoyl-4-(hydroxymethyl)glucoside | 147577-56-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4,6-dideoxy-2,3-dibenzoyl-4-(hydroxymethyl)glucoside
• 英文别名: [(2S,3R,4S,5R,6R)-3-benzoyloxy-5-(hydroxymethyl)-2-methoxy-6-methyloxan-4-yl] benzoate
• CAS: 147577-56-8
• 化学式: C₂₂H₂₄O₇
• 分子量: 400.428
• InChiKey: GCBNKAKALRLQLH-PTSOYHJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 4,6-dideoxy-2,3-dibenzoyl-4-(hydroxymethyl)glucoside 在 sodium hydroxide 、 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸酐 作用下， 以 甲醇 为溶剂， 反应 1.25h， 生成 (2S,3R,4S,5S,6R)-5-((2R,4S,5S,6R)-4,5-Dihydroxy-6-methyl-tetrahydro-pyran-2-yloxymethyl)-2-methoxy-6-methyl-tetrahydro-pyran-3,4-diol
  参考文献：
  名称：

  Analysis of Hydroxylamine Glycosidic Linkages: Structural Consequences of the NO Bond in Calicheamicin

  摘要：

  The antitumor activity of calicheamicin is related to its ability to bind to and cleave double-stranded DNA. There is substantial evidence that the oligosaccharide-aryl tail of calicheamicin plays a critical role in the binding selectivity. The calicheamicin oligosaccharide contains some unusual structural elements that may be related to the DNA binding function. A better understanding of how structure is related to function in the calicheamicin oligosaccharide could result in an ability to design new DNA binders. In this paper, the influence of the hydroxylamine glycosidic linkage on the shape of the calicheamicin oligosaccharide is analyzed in detail using a combination of experimental data and molecular mechanics calculations. As part of this work, parameters for N-O bonds have been developed for use with the program DISCOVER (AMBER force field). The analysis indicates that the unusual N-O bond in calicheamicin, with its distinctive torsion angle preferences, organizes the two halves of the molecule into a shape that complements the shape Of the minor groove.

  DOI：

  10.1021/ja00087a005
• 作为产物：
  描述：

  一氧化碳 、 [(2S,3R,4R,5R,6R)-3-benzoyloxy-5-iodo-2-methoxy-6-methyloxan-4-yl] benzoate 在 偶氮二异丁腈 、 三苯基氢化锗 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 苯 为溶剂， 105.0 ℃ 、9.65 MPa 条件下， 反应 12.0h， 以37%的产率得到methyl 4,6-dideoxy-2,3-dibenzoyl-4-(hydroxymethyl)glucoside
  参考文献：
  名称：

  Direct introduction of CH2OH by intermolecular trapping of CO

  摘要：

  Alkyl iodides are converted to the corresponding hydroxymethyl compounds in good yield by treatment with catalytic triphenylgermane-NaBH3CN-AIBN in benzene-THF under an atmosphere of CO at high pressure. This methodology is used for the synthesis of an analogue of the B ring of the calicheamicin oligosaccharide in which the hydroxylamine at C4 is replaced by a hydroxymethyl group.

  DOI：

  10.1016/s0040-4039(00)61627-1

文献信息

• Analysis of Hydroxylamine Glycosidic Linkages: Structural Consequences of the NO Bond in Calicheamicin
  作者：Suzanne Walker、Varsha Gupta、Daniel Kahne、David Gange

  DOI：10.1021/ja00087a005

  日期：1994.4

  The antitumor activity of calicheamicin is related to its ability to bind to and cleave double-stranded DNA. There is substantial evidence that the oligosaccharide-aryl tail of calicheamicin plays a critical role in the binding selectivity. The calicheamicin oligosaccharide contains some unusual structural elements that may be related to the DNA binding function. A better understanding of how structure is related to function in the calicheamicin oligosaccharide could result in an ability to design new DNA binders. In this paper, the influence of the hydroxylamine glycosidic linkage on the shape of the calicheamicin oligosaccharide is analyzed in detail using a combination of experimental data and molecular mechanics calculations. As part of this work, parameters for N-O bonds have been developed for use with the program DISCOVER (AMBER force field). The analysis indicates that the unusual N-O bond in calicheamicin, with its distinctive torsion angle preferences, organizes the two halves of the molecule into a shape that complements the shape Of the minor groove.
• Direct introduction of CH2OH by intermolecular trapping of CO
  作者：Varsha Gupta、Daniel Kahne

  DOI：10.1016/s0040-4039(00)61627-1

  日期：1993.1

  Alkyl iodides are converted to the corresponding hydroxymethyl compounds in good yield by treatment with catalytic triphenylgermane-NaBH3CN-AIBN in benzene-THF under an atmosphere of CO at high pressure. This methodology is used for the synthesis of an analogue of the B ring of the calicheamicin oligosaccharide in which the hydroxylamine at C4 is replaced by a hydroxymethyl group.