1,2,3,4-tetra-O-benzoyl-6-O-tert-butyldimethylsilyl-D-glucopyranoside | 590368-02-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,2,3,4-tetra-O-benzoyl-6-O-tert-butyldimethylsilyl-D-glucopyranoside
• 英文别名: (3R,4S,5R,6R)-6-(((tert-Butyldimethylsilyl)oxy)methyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl tetrabenzoate；[(2R,3R,4S,5R)-4,5,6-tribenzoyloxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]oxan-3-yl] benzoate
• CAS: 590368-02-8
• 化学式: C₄₀H₄₂O₁₀Si
• 分子量: 710.853
• InChiKey: AQLURWHBCUUICR-WNGVHCIWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  51
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,2,3,4-tetra-O-benzoyl-6-O-tert-butyldimethylsilyl-D-glucopyranoside 在 三氟甲磺酸三甲基硅酯 、 氨 、 potassium carbonate 、 决明内酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 26.0h， 生成 1,6-anhydro-2,3,4-tri-O-benzoyl-β-D-glucopyranose
  参考文献：
  名称：

  Total Synthesis of the Antiallergic Naphtho-α-pyrone Tetraglucoside, Cassiaside C₂, Isolated from Cassia Seeds

  摘要：

  Toralactone 9-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (1, cassiaside C-2) isolated from Cassia obtusifolia L. and showing strong antiallergic activity, was concisely synthesized employing glycosyl trifluoroacetimidates as glycosylation agents. The unique naphtho-alpha-pyrone structure of toralactone (5) was constructed by condensation of orsellinate 8 with pyrone 9 in the presence of LDA as developed by Staunton and co-workers. The naphthol of toralactone showed minimal reactivity as an acceptor and was screened with various glycosyl donors. It is finally concluded that sacrifice of an excess amount of the trifluoroacetimidate or trichloroacetimidate donors (6f/6g, 6.0 equiv) in the presence of a catalytic amount of TMSOTf (0.05 and 0.3 equiv, respectively) afforded excellent yields of the coupling product, which was otherwise only a minor product under a variety of conditions examined.

  DOI：

  10.1021/jo034223u
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 1,2,3,4-tetra-O-benzoyl-D-glucopyranoside 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以88%的产率得到1,2,3,4-tetra-O-benzoyl-6-O-tert-butyldimethylsilyl-D-glucopyranoside
  参考文献：
  名称：

  Total Synthesis of the Antiallergic Naphtho-α-pyrone Tetraglucoside, Cassiaside C₂, Isolated from Cassia Seeds

  摘要：

  Toralactone 9-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (1, cassiaside C-2) isolated from Cassia obtusifolia L. and showing strong antiallergic activity, was concisely synthesized employing glycosyl trifluoroacetimidates as glycosylation agents. The unique naphtho-alpha-pyrone structure of toralactone (5) was constructed by condensation of orsellinate 8 with pyrone 9 in the presence of LDA as developed by Staunton and co-workers. The naphthol of toralactone showed minimal reactivity as an acceptor and was screened with various glycosyl donors. It is finally concluded that sacrifice of an excess amount of the trifluoroacetimidate or trichloroacetimidate donors (6f/6g, 6.0 equiv) in the presence of a catalytic amount of TMSOTf (0.05 and 0.3 equiv, respectively) afforded excellent yields of the coupling product, which was otherwise only a minor product under a variety of conditions examined.

  DOI：

  10.1021/jo034223u

文献信息

• Isoquinoline-1-Carboxylate as a Traceless Leaving Group for Chelation-Assisted Glycosylation under Mild and Neutral Reaction Conditions
  作者：Hao-Yuan Wang、Christopher J. Simmons、Stephanie A. Blaszczyk、Paul G. Balzer、Renshi Luo、Xiyan Duan、Weiping Tang

  DOI：10.1002/anie.201708920

  日期：2017.12.4

  Glycosyl isoquinoline‐1‐carboxylate was developed as a novel benchtop stable and readily available glycosyl donor. The glycosylation reaction was promoted by the inexpensive Cu(OTf)2 salt under mild reaction conditions. The copper isoquinoline‐1‐carboxylate salt was precipitated from the solution and thus rendered a traceless leaving group. Surprisingly, the proton from the acceptor was absorbed by

  糖基异喹啉-1-羧酸被开发为一种新型的台式稳定且易于获得的糖基供体。在温和的反应条件下，廉价的Cu（OTf）2盐促进了糖基化反应。异喹啉-1-羧酸铜盐从溶液中沉淀出来，因此成为无痕的离去基团。令人惊讶地，来自受体的质子被沉淀的金属络合物吸收，并且反应混合物保持在中性pH。还证明了铜促进的糖基化与金促进的糖基化完全正交，并且在温和的反应条件下，可以从台式稳定的异头酯结构单元迭代合成寡糖。
• Total Synthesis of the Antiallergic Naphtho-α-pyrone Tetraglucoside, Cassiaside C₂, Isolated from Cassia Seeds
  作者：Zhaojun Zhang、Biao Yu

  DOI：10.1021/jo034223u

  日期：2003.8.1

  Toralactone 9-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (1, cassiaside C-2) isolated from Cassia obtusifolia L. and showing strong antiallergic activity, was concisely synthesized employing glycosyl trifluoroacetimidates as glycosylation agents. The unique naphtho-alpha-pyrone structure of toralactone (5) was constructed by condensation of orsellinate 8 with pyrone 9 in the presence of LDA as developed by Staunton and co-workers. The naphthol of toralactone showed minimal reactivity as an acceptor and was screened with various glycosyl donors. It is finally concluded that sacrifice of an excess amount of the trifluoroacetimidate or trichloroacetimidate donors (6f/6g, 6.0 equiv) in the presence of a catalytic amount of TMSOTf (0.05 and 0.3 equiv, respectively) afforded excellent yields of the coupling product, which was otherwise only a minor product under a variety of conditions examined.