2-acetamido-2-deoxy-3,4-O-isopropylidene-D-glucose dimethyl acetal | 73707-70-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-acetamido-2-deoxy-3,4-O-isopropylidene-D-glucose dimethyl acetal
• 英文别名: 2-Acetamido-2-deoxy-3,4-O-isopropylidine-aldehydo-D-glucose dimethyl acetal；N-[(1R)-1-[(4R,5R)-5-[(1R)-1,2-dihydroxyethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethoxyethyl]acetamide
• CAS: 73707-70-7
• 化学式: C₁₃H₂₅NO₇
• 分子量: 307.344
• InChiKey: IGPHWZFBILYQBD-GWOFURMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.5
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  107
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-acetamido-2-deoxy-3,4-O-isopropylidene-D-glucose dimethyl acetal 在 ruthenium trichloride 、 sodium periodate 、 氯化亚砜 、 三乙胺 作用下， 以 四氯化碳 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 3.0h， 生成 N-[(1R)-1-[(4R,5S)-5-[(4R)-2,2-dioxo-1,3,2-dioxathiolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethoxyethyl]acetamide
  参考文献：
  名称：

  Applications of Cyclic Sulfates of vic-Diols:  Synthesis of Episulfides, Olefins, and Thio Sugars

  摘要：

  A new efficient and expeditious one-pot synthesis of thiiranes and olefins from cyclic sulfates of vic-diols is described. Opening of cyclic sulfates with potassium thioacetate or potassium thiocyanate followed by treatment with sodium methoxide led to episulfides. Olefins were obtained when potassium selenocyanate was used as nucleophile, and the obtained monoesters were treated with sodium borohydride. This method was applied to acyclic polyols derived from chiral glycerine, 1,2-isopropylidenehexofuranoses with different subtituents at C-3, and dimethyl acetals derived from pentoses and hexoses. The methodology is highly versatile, and its applicability has been demonstrated by the synthesis of different 4- and 5-thiosugars by opening of the thiirane ring with sodium acetate or lithium aluminum hydride. Reduction with lithium aluminum hydride of the thiocyanate sulfate potassium salt obtained by the opening of cyclic sulfate with KSCN allowed the direct synthesis of 5-deoxy-4-thio- and 6-deoxy-5-thiosugars. Cyclic thiosugars with the sulfur atom in the ring are obtained by acidic hydrolysis of the 5-thiol derivatives of 1,2-O-isopropylidenehexofuranoses and 4-thiopentose dimethyl acetals. Using this method, an efficient synthesis of 5-thio-L-fucose as well as the synthesis of 2,5-dideoxy-4-thiofuranose is described.

  DOI：

  10.1021/jo962066b
• 作为产物：
  描述：

  N-[(R)-2,2-Dimethoxy-1-((4S,5R,4'R)-2,2,2',2'-tetramethyl-[4,4']bi[[1,3]dioxolanyl]-5-yl)-ethyl]-acetamide 在 溶剂黄146 作用下， 以 水 为溶剂， 反应 2.0h， 以81%的产率得到2-acetamido-2-deoxy-3,4-O-isopropylidene-D-glucose dimethyl acetal
  参考文献：
  名称：

  新的化学报告基因 6-Alkynyl-6-deoxy-GlcNAc 揭示了可阻断 Caspase-8 裂解/激活的凋亡 Caspase 的 O-GlcNAc 修饰

  摘要：

  O-GlcNAc 修饰（O-GlcNAcylation）是哺乳动物细胞存活所必需的。遗传和生化实验发现，增加的修饰会抑制组织和细胞培养中的细胞凋亡，而降低 O-GlcNAcylation 会诱导细胞死亡。然而，O-GlcNAcylation 可能抑制细胞凋亡的分子机制仍在阐明。在这里，我们首先合成了一种新的代谢化学报告基因 6-Alkynyl-6-deoxy-GlcNAc (6AlkGlcNAc)，用于鉴定 O-GlcNAc 修饰的蛋白质。6AlkGlcNAc 的后续表征表明，该探针通过细胞表面糖蛋白选择性地掺入 O-GlcNAcylated 蛋白中。使用这个探针，我们发现凋亡的半胱天冬酶是 O-GlcNAcylated，我们使用其他技术证实了这一点，提高了修饰影响其生物化学的可能性。然后我们证明 O-GlcNAcylation 全局水平的变化导致细胞凋亡过程中 caspase-8 激活动力学的相反变化。最后，我们表明

  DOI：

  10.1021/jacs.7b02213

文献信息

• One-flask synthesis of triacetalated aldohexoses with 2,2-dialkoxypropane and p-toluenesulfonic acid
  作者：Makoto Kiso、Akihiro Kondo、Yumi Kondo、Akira Hasegawa

  DOI：10.1016/0008-6215(84)85110-1

  日期：1984.4

  - arabino -hexose and some N -protected 2-amino-2-deoxy- d -glucose derivatives were each treated with 2,2-dimethoxy- or 2,2-dibenzyloxy-propane in 1,4-dioxane in the presence of p -toluenesulfonic acid at 60–70°. The major products were acyclic, dimethyl and dibenzyl acetals of 2-deoxy-3,4:5,6-di- O -isopropylidene- aldehydo - d - arabino -hexose or of N -protected 2-amino-2-deoxy-3,4:5,6-di- O -isopropylidene-

  摘要将2-脱氧-d-阿拉伯糖己糖和一些N-保护的2-氨基-2-脱氧-d-葡萄糖衍生物分别在1,4-中用2,2-二甲氧基或2,2-二苄氧基丙烷处理。在对甲苯磺酸存在下于60–70°下形成二恶烷。主要产物是2-脱氧-3,4：5,6-二-O-异亚丙基-醛-d-阿拉伯糖-己糖或N-保护的2-氨基-2-脱氧-3的无环，二甲基和二苄基缩醛，4：5,6-二-O-异亚丙基-醛-d-葡萄糖。一些二苄基乙缩醛以良好的产率转化为相应的3,4：5,6-二-O-异亚丙基-醛-d-己糖。
• Synthesis of 2-Acetamido-2,5-dideoxy-5-phosphoryl-D-glucopyranose Derivatives: New Phospha-sugar Analogs of N-Acetyl-D-glucosamine
  作者：Tadashi Hanaya、Masahiro Kawaguchi、Masakazu Sumi、Kazuo Makino、Keiko Tsukada、Hiroshi Yamamoto

  DOI：10.3987/com-12-s(n)69

  日期：——

  Starting with N-acetyl-D-glucosamine, methyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-beta-D-xylo-hexofuranosid-5-ulose (18) was prepared in 7 steps. The addition reaction of dimethyl phosphonate to 18, followed by deoxygenation of its 5-hydroxy group, provided the 5-deoxy-5-dimethoxyphosphoryl-D-glucofuranoside derivative (21a). The hydride reduction of 21a, followed by the action of hydrochloric acid and then hydrogen peroxide, afforded the first D-glucosamine analog (23) having a phosphoryl group in the hemiacetal ring. This was converted into the per-O-acetylated N-acetyl-D-glucosamine phospha-sugar (25), while the same treatment of the 5-deoxy-5-dimethoxyphosphoryl-L-idose dimethyl acetal derivative (13b) afforded the N-acetyl-L-idosamine phospha-sugar (29).
• A facile synthesis of 2-acetamido-2-deoxy-5-thio-d-glucopyranose
  作者：Eiji Tanahashi、Makoto Kiso、Akira Hasegawa

  DOI：10.1016/0008-6215(83)88098-7

  日期：1983.6
• Applications of Cyclic Sulfates of <i>vic</i>-Diols:  Synthesis of Episulfides, Olefins, and Thio Sugars
  作者：Francisco G. Calvo-Flores、Pilar García-Mendoza、Fernando Hernández-Mateo、Joaquín Isac-García、Francisco Santoyo-González

  DOI：10.1021/jo962066b

  日期：1997.6.13

  A new efficient and expeditious one-pot synthesis of thiiranes and olefins from cyclic sulfates of vic-diols is described. Opening of cyclic sulfates with potassium thioacetate or potassium thiocyanate followed by treatment with sodium methoxide led to episulfides. Olefins were obtained when potassium selenocyanate was used as nucleophile, and the obtained monoesters were treated with sodium borohydride. This method was applied to acyclic polyols derived from chiral glycerine, 1,2-isopropylidenehexofuranoses with different subtituents at C-3, and dimethyl acetals derived from pentoses and hexoses. The methodology is highly versatile, and its applicability has been demonstrated by the synthesis of different 4- and 5-thiosugars by opening of the thiirane ring with sodium acetate or lithium aluminum hydride. Reduction with lithium aluminum hydride of the thiocyanate sulfate potassium salt obtained by the opening of cyclic sulfate with KSCN allowed the direct synthesis of 5-deoxy-4-thio- and 6-deoxy-5-thiosugars. Cyclic thiosugars with the sulfur atom in the ring are obtained by acidic hydrolysis of the 5-thiol derivatives of 1,2-O-isopropylidenehexofuranoses and 4-thiopentose dimethyl acetals. Using this method, an efficient synthesis of 5-thio-L-fucose as well as the synthesis of 2,5-dideoxy-4-thiofuranose is described.
• The New Chemical Reporter 6-Alkynyl-6-deoxy-GlcNAc Reveals O-GlcNAc Modification of the Apoptotic Caspases That Can Block the Cleavage/Activation of Caspase-8
  作者：Kelly N. Chuh、Anna R. Batt、Balyn W. Zaro、Narek Darabedian、Nicholas P. Marotta、Caroline K. Brennan、Arya Amirhekmat、Matthew R. Pratt

  DOI：10.1021/jacs.7b02213

  日期：2017.6.14

  new metabolic chemical reporter, 6-Alkynyl-6-deoxy-GlcNAc (6AlkGlcNAc), for the identification of O-GlcNAc-modified proteins. Subsequent characterization of 6AlkGlcNAc shows that this probe is selectively incorporated into O-GlcNAcylated proteins over cell-surface glycoproteins. Using this probe, we discover that the apoptotic caspases are O-GlcNAcylated, which we confirmed using other techniques,

  O-GlcNAc 修饰（O-GlcNAcylation）是哺乳动物细胞存活所必需的。遗传和生化实验发现，增加的修饰会抑制组织和细胞培养中的细胞凋亡，而降低 O-GlcNAcylation 会诱导细胞死亡。然而，O-GlcNAcylation 可能抑制细胞凋亡的分子机制仍在阐明。在这里，我们首先合成了一种新的代谢化学报告基因 6-Alkynyl-6-deoxy-GlcNAc (6AlkGlcNAc)，用于鉴定 O-GlcNAc 修饰的蛋白质。6AlkGlcNAc 的后续表征表明，该探针通过细胞表面糖蛋白选择性地掺入 O-GlcNAcylated 蛋白中。使用这个探针，我们发现凋亡的半胱天冬酶是 O-GlcNAcylated，我们使用其他技术证实了这一点，提高了修饰影响其生物化学的可能性。然后我们证明 O-GlcNAcylation 全局水平的变化导致细胞凋亡过程中 caspase-8 激活动力学的相反变化。最后，我们表明