3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl chloride | 134665-28-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl chloride
• 英文别名: 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbamyl)-α-D-glucopyranosyl chloride；TrocNH(-2d)a-Glc1Cl3Ac4Ac6Ac；[(2R,3S,4R,5R,6R)-3,4-diacetyloxy-6-chloro-5-(2,2,2-trichloroethoxycarbonylamino)oxan-2-yl]methyl acetate
• CAS: 134665-28-4
• 化学式: C₁₅H₁₉Cl₄NO₉
• 分子量: 499.129
• InChiKey: NJIPBZFLXVTRFQ-VEGXAWMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  127
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl chloride 在 甲醇 、 silver trifluoromethanesulfonate 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 40.17h， 生成 diosgenyl 2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside
  参考文献：
  名称：

  Differently N-protected 3,4,6-tri-O-acetyl-2-amino-2-deoxy-d-glucopyranosyl chlorides and their application in the synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside

  摘要：

  Four differently N-protected 3,4,6-tri-O-acetyl-2-amino-2-deoxy-D-glucopyranosyl chlorides were synthesized and used as glycosyl donors in reactions with diosgenin. The following amine group protections were tested: trifluoroacetyl (TFA), 2,2,2-trichloroethoxycarbonyl (Troc), phthaloyl (Phth), and tetrachlorophthaloyl (TCP). Products of glycosylation were deprotected to yield diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside. The efficiency of the procedures is discussed. Additionally, a single-crystal X-ray diffraction analysis for 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranosyl chloride is reported. Orientations of the pyranose substituents as well as the planarity of the acetoxy and phthalimide groups in the crystal lattice are discussed. Structural evidence is presented for a mesomeric effect in both groups. The preference of the cis over trans orientation of the acetoxy group is confirmed in the crystal lattice. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2012.11.020
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α,β-D-glucopyranose 在 三聚氯氰 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N-二甲基甲酰胺 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 以75%的产率得到3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl chloride
  参考文献：
  名称：

  A mild and general method for preparation of α-glycosyl chlorides

  摘要：

  A mild and efficient chlorination method for production of glycosyl chlorides is first described which employs inexpensive trichlorotriazine (TCT) and DMF as a chlorination reagent and is compatible with typical acid-labile hydroxyl protecting functions. The scope and limitations, reaction mechanism and its application in the sequential glycosylations are discussed. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.05.077

文献信息

• Conversion of p-methoxyphenyl glycosides into the corresponding glycosyl chlorides and bromides, and into thiophenyl glycosides
  作者：Zhiyuan Zhang、Göran Magnusson

  DOI：10.1016/s0008-6215(96)90118-4

  日期：1996.12

  Treatment of the pMP glycosides with acyl chlorides or bromides in the presence of various Lewis acids gave the corresponding glycosyl chlorides and bromides in 81-98% yield. Treatment of the acyl-protected pMP glycosides with thiophenol and boron trifluoride etherate gave the corresponding thioglycosides in 80-100% yield and high (> 20:1) beta/alpha selectivity. The stability of pMP glycosides was investigated

  使用硼从相应的1-O-乙酰基糖中制备对甲氧基苯基（pMP）β-D-吡喃葡萄糖苷（Glc，Gal，GlcNPhth，GalNPhth，GlcNTroc，Gal beta 4Glc，Gal alpha 4Gal），使用硼制得三氟化醚醚为助催化剂。在各种路易斯酸的存在下用酰氯或溴化物处理pMP糖苷得到相应的糖酰氯和溴化物，产率为81-98％。用硫酚和三氟化硼醚化物处理酰基保护的pMP糖苷，可以80-100％的收率和高（> 20：1）β/ alpha选择性获得相应的硫糖苷。针对一系列试剂研究了pMP糖苷的稳定性。
• A novel glycoside anomerization catalyzed by trimethylsilyl bromide and zinc bromide in combination.
  作者：Kunio HIGASHI、Kiyoshi NAKAYAMA、Kouichi UOTO、Emiko SHIOYA、Tsuneo KUSAMA

  DOI：10.1248/cpb.39.590

  日期：——

  A novel glycoside anomerization occurred when trimethylsilyl bromide (TMSBr) and zinc bromide were utilized in combination as a catalyst. Treatment of β-glycosides with TMSBr and zinc bromide in the presence of alcohols afforded anomerized products in good yields.

  当三甲基溴硅烷（TMSBr）和溴化锌组合用作催化剂时，发生了一种新型的糖苷异构化反应。在醇存在下，用 TMSBr 和溴化锌处理 β-糖苷，可得到良好产率的异构化产物。