methyl O-<3,4,6-tri-O-acetyl-2-deoxy-(2,2,2-trichloroethoxycarbonyl)amino)-β-D-glucopyranosyl>-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside | 145383-38-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl O-<3,4,6-tri-O-acetyl-2-deoxy-(2,2,2-trichloroethoxycarbonyl)amino)-β-D-glucopyranosyl>-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-acetyl-2-(2,2,2-trichloroethoxycarbonylamino)-2-deoxy-β-D-glucopyranosyl)-α-D-glucopyranoside；methyl O-(3,4,6-tri-O-acetyl-2-deoxy-2-trichloroethoxycarbamoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl (3,4,6-tri-O-acetyl-2-deoxy-2-trichloroethoxycarbamoyl-β-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 6-O-(3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxy)carbamoyl-β-D-glucopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；TrocNH(-2d)Glc3Ac4Ac6Ac(b1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；[(2R,3S,4R,5R,6R)-3,4-diacetyloxy-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-5-(2,2,2-trichloroethoxycarbonylamino)oxan-2-yl]methyl acetate
• CAS: 145383-38-6
• 化学式: C₄₃H₅₀Cl₃NO₁₅
• 分子量: 927.227
• InChiKey: VJSKCJYVLPOUQD-CPHBXOIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  62
• 可旋转键数：
  23
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.49
• 拓扑面积：
  182
• 氢给体数：
  1
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 methyl O-<3,4,6-tri-O-acetyl-2-deoxy-(2,2,2-trichloroethoxycarbonyl)amino)-β-D-glucopyranosyl>-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside 在 锌 作用下， 反应 5.0h， 以84%的产率得到methyl O-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  N-三氯乙氧基羰基-葡萄糖胺衍生物作为糖基供体。

  摘要：

  D-葡萄糖胺可以容易地转化为1,3,4,6-四-O-乙酰基-2-脱氧-2-（2,2,2-三氯乙氧基羰基氨基++）-D-吡喃葡萄糖（2）。从该中间体可以得到有价值的糖基供体。在三氟化硼醚化物存在下与乙硫醇反应得到乙基3,4,6-三-O-乙酰基-2-脱氧-1-硫-2-（2,2,2-三氯乙氧基羰基氨基）-β-D-吡喃葡萄糖苷（ 4），经N-乙酰化得到N-乙酰基-N-三氯乙氧基羰基衍生物（5）。在2中选择性除去1-O-乙酰基，然后在碱存在下用三氯乙腈处理，得到3,4,6-三-O-乙酰基-2-脱氧-2-（2,2,2-三氯乙氧基羰基氨基） -α-D-吡喃葡萄糖基三氯乙酰亚胺酸酯（6）。在N-碘代琥珀酰亚胺/三氟甲磺酸作为促进剂体系存在下，5与5个被选择性保护的糖苷作为糖基受体的反应以良好的产率提供了相应的β-糖苷，因此显示出5的有价值的糖基供体性质。 （Teoc）基团以高收率提供了相应的N-乙酰基保护

  DOI：

  10.1016/s0008-6215(96)00237-6
• 作为产物：
  描述：

  在 三氟甲磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 4.08h， 生成 methyl O-<3,4,6-tri-O-acetyl-2-deoxy-(2,2,2-trichloroethoxycarbonyl)amino)-β-D-glucopyranosyl>-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  稳定硫代糖苷供体的酸催化O-糖基化

  摘要：

  两类硫代糖苷（4-（4-甲氧基苯基）-3-丁烯基硫代糖苷（MBTG）和4-（4-甲氧基苯基）-4-戊烯基硫代糖苷（MPTG））经过酸催化的O-糖基化反应，并带有一系列糖和非糖醇在25°C下。苯乙烯烯烃上的电子密度对于反应性至关重要，而糖保护基的作用则微乎其微。与大多数硫糖苷活化方法相反，MBTG的酸催化活化与电子中性烯烃相容。

  DOI：

  10.1021/acs.orglett.8b02125

文献信息

• An Air- and Water-Stable Iodonium Salt Promoter for Facile Thioglycoside Activation
  作者：An-Hsiang Adam Chu、Andrei Minciunescu、Vittorio Montanari、Krishna Kumar、Clay S. Bennett

  DOI：10.1021/ol5004059

  日期：2014.3.21

  iodonium salt phenyl(trifluoroethyl)iodonium triflimide is shown to activate thioglycosides for glycosylation at room temperature. Both armed and disarmed thioglycosides rapidly undergo glycosylation in 68–97% yield. The reaction conditions are mild and do not require strict exclusion of air and moisture. The operational simplicity of the method should allow experimentalists with a limited synthetic background

  空气和水稳定的碘鎓盐苯基（三氟乙基）碘鎓三氟甲磺酰亚胺在室温下可激活硫代糖苷以进行糖基化。武装和解除武装的硫糖苷都以 68-97% 的产率迅速进行糖基化。反应条件温和，不需要严格排除空气和水分。该方法的操作简单性应该允许具有有限合成背景的实验者构建糖苷键。
• S-Benzimidazolyl Glycosides as a Platform for Oligosaccharide Synthesis by an Active-Latent Strategy
  作者：Scott J. Hasty、Matthew A. Kleine、Alexei V. Demchenko

  DOI：10.1002/anie.201007212

  日期：2011.4.26

  for glycosylation under a variety of conditions, including metal‐assisted and alkylation pathways. Application of a substituted SBiz moiety (X=anisoyl, see picture) allows active–latent and armed–disarmed types of oligosaccharide assembly.

  开展业务：S-苯并咪唑基 (SBiz) 异头部分是一种新的离去基团，可以在多种条件下被激活进行糖基化，包括金属辅助和烷基化途径。应用取代的 SBiz 部分（X=苯甲酰基，见图）可实现活性-潜在和武装-解除武装类型的寡糖组装。
• Catalytic Stereoselective Synthesis of 2-Amino-2-Deoxy-α-D-Glucopyranosides and Galactopyranosides
  作者：Koki Matsubara、Teruaki Mukaiyama

  DOI：10.1246/cl.1993.2145

  日期：1993.12

  In the presence of a catalyst generated from SnCl4 and a silver salt, various 2-amino-2-deoxy-α-D-glucopyranosides or galactopyranosides are stereoselectively synthesized in good yields with high stereoselectivities through anomerization step starting from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranose or galactopyranose and alkyl trimethylsilyl ethers, respectively.

  在 SnCl4 和银盐生成的催化剂存在下，通过从 1,3,4 开始的异构化步骤，立体选择性地以良好的产率和高立体选择性合成了各种 2-氨基-2-脱氧-α-D-吡喃葡萄糖苷或吡喃半乳糖苷，分别为6-四-O-乙酰基-2-脱氧-2-(2,2,2-三氯乙氧基羰基氨基)-β-D-吡喃葡萄糖或吡喃半乳糖和烷基三甲基甲硅烷基醚。
• Stereoselective Synthesis of 2-Amino-2-deoxy-β-D-glucopyranosides and Galactopyranosides by Using a Catalytic Amount of Tin(II) Trifluoromethanesulfonate
  作者：Teruaki Mukaiyama、Koki Matsubara

  DOI：10.1246/cl.1992.1755

  日期：1992.9

  In the presence of a catalytic amount of tin(II) trifluoromethanesulfonate, various 2-amino-2-deoxy-β-D-glucopyranosides or galactopyranosides are stereoselectively synthesized in good yields from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxy carbonylamino)-β-D-glucopyranose or galactopyranose and alkyl trimethylsilyl ethers, respectively.

  在催化量的三氟甲磺酸锡（II）存在下，可分别从 1,3,4,6-四-O-乙酰基-2-脱氧-2-(2,2,2-三氯乙氧基羰基氨基)-β-D-吡喃葡萄糖或吡喃半乳糖苷和烷基三甲基硅醚立体选择性地合成各种 2-氨基-2-脱氧-β-D-吡喃葡萄糖苷或吡喃半乳糖苷，且产率良好。
• Chemoselective Synthesis of Oligosaccharides of 2-Deoxy-2-aminosugars
  作者：Aileen F. G. Bongat、Medha N. Kamat、Alexei V. Demchenko

  DOI：10.1021/jo062171d

  日期：2007.2.1

  Along with the application of the S-benzoxazolyl glycosides to the high-yielding synthesis of disaccharides of the 2-amino-2-deoxy series, chemoselective assembly of oligosaccharides containing multiple residues of 2-amino-2-deoxyglycoses is reported. This modified armed-disarmed approach is relying on the observation that 2-N-trichloroethoxycarbonyl derivatives of S-benzoxazolyl glycosides are significantly more reactive than their 2-N-phthaloyl counterparts in MeOTf-promoted glycosylations. This allowed efficient chemoselective synthesis of 1,2-trans-linked oligosaccharides, the disarmed reducing end of which can be activated for immediate second step glycosidation in the presence of a more powerful activator, AgOTf. As a result of this two-step activation, trans-trans-patterned trisaccharides could be assembled in a highly efficient manner. This result differs from the classic armed-disarmed technique, according to which usually cis-trans-patterned oligosaccharides are generated.