6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-galactopyranoside trichloroacetimidate | 1310050-42-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-galactopyranoside trichloroacetimidate
• 英文别名: 6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate；[(2R,3R,4R,5R,6R)-5-azido-3,4-bis(phenylmethoxy)-6-(2,2,2-trichloroethanimidoyl)oxyoxan-2-yl]methyl acetate
• CAS: 1310050-42-0
• 化学式: C₂₄H₂₅Cl₃N₄O₆
• 分子量: 571.845
• InChiKey: ZLPSPCBQPLCOIH-QMCAAQAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  甲基2,3,4-三-O-苯甲酰-α-D-吡喃葡萄糖苷 、 6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-galactopyranoside trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 生成 [(2R,3R,4S,5R,6S)-2-[[(2R,3R,4R,5R,6R)-6-(acetyloxymethyl)-3-azido-4,5-bis(phenylmethoxy)oxan-2-yl]oxymethyl]-4,5-dibenzoyloxy-6-methoxyoxan-3-yl] benzoate 、 [(2R,3R,4S,5R,6S)-2-[[(2S,3R,4R,5R,6R)-6-(acetyloxymethyl)-3-azido-4,5-bis(phenylmethoxy)oxan-2-yl]oxymethyl]-4,5-dibenzoyloxy-6-methoxyoxan-3-yl] benzoate
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157
• 作为产物：
  描述：

  (2S,4aR,7R,8R,8aR)-7-azido-2-phenyl-6-(p-tolylthio)hexahydropyrano[3,2-d][1,3]dioxin-8-ol 在 N-溴代丁二酰亚胺(NBS) 、 硼烷四氢呋喃络合物 、 三氟甲磺酸三甲基硅酯 、 水 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 6.5h， 生成 6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-galactopyranoside trichloroacetimidate
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157

文献信息

• Gram scale synthesis of A (type 2) and B (type 2) blood group tetrasaccharides through 1,6-anhydro-N-acetyl-β-D-glucosamine
  作者：Tatiana V. Tyrtysh、Elena Yu. Korchagina、Ivan M. Ryzhov、Nicolai V. Bovin

  DOI：10.1016/j.carres.2017.06.014

  日期：2017.9

  Fuc-Gal-anhydroGlcNAc with single free 3'-OH group. Its standard α-galactosylation gave protected B (type 2) tetrasaccharide. For synthesis of correspondent A tetrasaccharide seven different 2-azido-2-deoxygalactosyl (GalN3) donors were tested: 6-O-acetyl-3,4-O-isopropylidene-GalN3 thioglycoside was shown to provide the best yield (89%) and stereoselectivity (α/β = 24:1). Further 1,6-anhydro cycle opening

  从3-O-苯甲酰基-1，6-脱水-N-乙酰基葡糖胺开始，提出了以3-氨基丙基糖苷形式的A（2型）和B（2型）四糖的革兰氏合成。其半乳糖基化，然后再保护，得到具有单个游离2'-OH基团的乳糖胺衍生物，总产率为75％。标准岩藻糖基化和下一轮再保护的总产率为88％，得到具有单个游离3'-OH基团的三糖Fuc-Gal-anhydroGlcNAc。其标准的α-半乳糖基化得到保护的B（2型）四糖。为了合成对应的A四糖，测试了七个不同的2-叠氮基-2-脱氧半乳糖基（GalN3）供体：6-O-乙酰基-3,4-O-异亚丙基-GalN3硫代糖苷提供了最佳收率（89％），立体选择性（α/β= 24：1）。进一步打开1,6-脱水循环，