tert-butyldiphenylsilyl 3,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-β-D-glucopyranoside | 1017587-58-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyldiphenylsilyl 3,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-β-D-glucopyranoside
• 英文别名: N-[(2S,3R,4R,5S,6R)-2-[tert-butyl(diphenyl)silyl]oxy-5-hydroxy-4-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]-2,2,2-trichloroacetamide
• CAS: 1017587-58-4
• 化学式: C₃₈H₄₂Cl₃NO₆Si
• 分子量: 743.199
• InChiKey: NBVPRIDIPOQPNW-JSMUHSIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.31
• 重原子数：
  49
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tert-butyldiphenylsilyl 3,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-β-D-glucopyranoside 、 phenyl 2,3,4-tri-O-benzyl-6-O-(4-methoxyphenyl)methyl-1-thio-β-D-galactopyranoside 在 1-(苯基亚硫酰基)哌啶 、 2,4,6-三叔丁基嘧啶 、 三氟甲磺酸酐 作用下， 以 丙腈 为溶剂， 反应 0.5h， 以71%的产率得到t-butyldiphenylsilyl 2,3,4-tri-O-benzyl-6-O-(4-methoxyphenyl)methyl-β-D-galactopyranosyl-(1->4)-3,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-β-D-glucopyranoside
  参考文献：
  名称：

  Solid-phase synthesis of O-sulfated glycopeptide by the benzyl-protected glycan strategy

  摘要：

  To expand the repertoire of our benzyl-protection strategy for solid-phase glycopeptide synthesis, an C-sulfated glycopeptide was chosen as the synthetic target. Trisaccharyl serine derivatives (Gal beta 1-4-GlcNAc beta 1-2-Many alpha 1-3-Ser) carrying (4-methoxyphenyl)methyl (MPM) groups at either 3-O or 6-O of the Gal residue were prepared through three stereoselective glycosylations. Cleavage of MPM followed by reaction with Me3N center dot SO3 efficiently afforded 3-O- and 6-O-sulfo-glycoserines, respectively. A preliminary debenzylation Study using the sulfated glycoserines revealed that the sulfate groups persisted under 'low-acidity TfOH' conditions, when using a limited amount of TfOH and extending the reaction period. The 3-O-sulfo-glycoserine was then introduced into an icosapeptide modeled after an alpha-dystroglycan fragment by a combination of automated and manual solid-phase peptide synthesis procedures. The synthesized glycopeptide was successfully debenzylated by the low-acidity TfOH cocktail with slight damage to the sulfate functionality. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.07.080
• 作为产物：
  描述：

  tert-butyldiphenylsilyl 3,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-4-O-trichloroacetyl-β-D-glucopyranoside 在 吡啶 作用下， 以 水 为溶剂， 反应 3.0h， 以98%的产率得到tert-butyldiphenylsilyl 3,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-β-D-glucopyranoside
  参考文献：
  名称：

  Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation

  摘要：

  beta-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.01.029

文献信息

• Synthesis of Biantennary Complex-Type Nonasaccharyl Asn Building Blocks for Solid-Phase Glycopeptide Synthesis
  作者：Masashi Hagiwara、Mizuki Dohi、Yuko Nakahara、Keiko Komatsu、Yuya Asahina、Akiharu Ueki、Hironobu Hojo、Yoshiaki Nakahara、Yukishige Ito

  DOI：10.1021/jo200149d

  日期：2011.7.1

  synthesized in a protected form suitable to use in the Fmoc solid-phase peptide synthesis studies. Two approaches for the nonasaccharide synthesis were examined by taking advantage of the highly β-selective glycosylation with GlcNTCA (N-phenyl)trifluoroacetimidate. An earlier approach, which involved the reaction of the trisaccharide donor (Gal-GlcNTCA-Man) and trisaccharide acceptor (Man-GlcNPhth2-N3), produced

  以适合于Fmoc固相肽合成研究的受保护形式合成带有LacNAc和LacdiNAc作为非还原末端基序的双天线复合型N-聚糖。通过利用GlcNTCA（N-苯基）三氟乙酰亚氨酸酯的高度β-选择性糖基化作用，研究了两种合成九糖的方法。较早的方法涉及三糖供体（Gal-GlcNTCA-Man）和三糖受体（Man-GlcNPhth 2 -N 3）的反应，产生了九糖异构体的混合物。另一方面，三糖受体的甘露糖基化（Man-GlcNPhth 2 -N 3）立体选择性地得到已知的五糖（Man 3 -GlcNPhth 2 -N 3），其与二糖基糖基供体（Gal-GlcNTCA或GalNTCA-GlcNTCA）反应以产生所需的九糖为单个立体异构体。选择性脱酞酰化，然后进行N-乙酰化，提供了GlcNAc 2的功能。在Ph（CH 3）2 P和HOOBt存在下，将所得的非糖基叠氮化物与Fmoc-Asp（OPfp）-OBu
• Chemoenzymatic Synthesis of Hydrophobic Glycoprotein: Synthesis of Saposin C Carrying Complex-Type Carbohydrate
  作者：Hironobu Hojo、Hiromasa Tanaka、Masashi Hagiwara、Yuya Asahina、Akiharu Ueki、Hidekazu Katayama、Yuko Nakahara、Azusa Yoneshige、Junko Matsuda、Yukishige Ito、Yoshiaki Nakahara

  DOI：10.1021/jo3010155

  日期：2012.11.2

  The complex-type N-linked octasaccharide oxazoline having LacNAc as the nonreducing end sugar was efficiently synthesized using the benzyl-protected LacNAc, mannose, and β-mannosyl GlcNAc units as key building blocks. To achieve a highly β-selective glycosylation with the LacNAc unit, the N-trichloroacetyl group was used for the protection of the amino group in the LacNAc unit. After complete assembly

  使用苄基保护的LacNAc，甘露糖和β-甘露糖基GlcNAc单元作为关键构件，有效合成了以LacNAc为非还原性末端糖的复合型N联八糖恶唑啉。为了实现与LacNAc单元的高度β-选择性糖基化，将N-三氯乙酰基用于保护LacNAc单元中的氨基。这些单元完全组装并脱保护后，将获得的游离糖成功衍生为相应的糖恶唑啉。另一方面，N通过天然的化学连接反应化学合成了疏水性脂质结合蛋白β-乙酰基氨基葡萄糖酰化的saposinC。基于与非糖基化saposin C的合成有关的先前结果，将O-酰基异肽结构引入带有GlcNAc的N-末端肽硫酯，以改善其对水性有机溶剂的溶解性。在O-酰基异肽部分同时发生O-至N-酰基转移的同时，连接反应有效地进行。除去半胱氨酸保护基并折叠后，成功获得了携带Saposin C的GlcNAc。然后，使用endo-β- N突变体将合成的糖恶唑啉转移到该糖蛋白上成功地获得了来自Mucor
• Solid-phase synthesis of O-sulfated glycopeptide by the benzyl-protected glycan strategy
  作者：Keita Kawahira、Hiromasa Tanaka、Akiharu Ueki、Yuko Nakahara、Hironobu Hojo、Yoshiaki Nakahara

  DOI：10.1016/j.tet.2009.07.080

  日期：2009.9

  To expand the repertoire of our benzyl-protection strategy for solid-phase glycopeptide synthesis, an C-sulfated glycopeptide was chosen as the synthetic target. Trisaccharyl serine derivatives (Gal beta 1-4-GlcNAc beta 1-2-Many alpha 1-3-Ser) carrying (4-methoxyphenyl)methyl (MPM) groups at either 3-O or 6-O of the Gal residue were prepared through three stereoselective glycosylations. Cleavage of MPM followed by reaction with Me3N center dot SO3 efficiently afforded 3-O- and 6-O-sulfo-glycoserines, respectively. A preliminary debenzylation Study using the sulfated glycoserines revealed that the sulfate groups persisted under 'low-acidity TfOH' conditions, when using a limited amount of TfOH and extending the reaction period. The 3-O-sulfo-glycoserine was then introduced into an icosapeptide modeled after an alpha-dystroglycan fragment by a combination of automated and manual solid-phase peptide synthesis procedures. The synthesized glycopeptide was successfully debenzylated by the low-acidity TfOH cocktail with slight damage to the sulfate functionality. (C) 2009 Elsevier Ltd. All rights reserved.
• Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation
  作者：Akiharu Ueki、Masafumi Hirota、Yuta Kobayashi、Keiko Komatsu、Yutaka Takano、Michio Iwaoka、Yuko Nakahara、Hironobu Hojo、Yoshiaki Nakahara

  DOI：10.1016/j.tet.2008.01.029

  日期：2008.3

  beta-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. (c) 2008 Elsevier Ltd. All rights reserved.