benzyl 2,3,4-tri-O-benzyl-1-O-(trichloroacetimidoyl)-α-D-glucopyranuronate | 184698-69-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 2,3,4-tri-O-benzyl-1-O-(trichloroacetimidoyl)-α-D-glucopyranuronate
• 英文别名: benzyl 1-O-trichloroacetimidoyl-2,3,4-tri-O-benzyl-α-D-glucopyranuronate；Benzyl (2S,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-2-carboxylate；benzyl (2S,3S,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(2,2,2-trichloroethanimidoyl)oxyoxane-2-carboxylate
• CAS: 184698-69-9
• 化学式: C₃₆H₃₄Cl₃NO₇
• 分子量: 699.027
• InChiKey: BPINMQTUNMBWAP-FVRGGSDBSA-N

物化性质

• 沸点：
  701.4±70.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  47
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  96.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-O-benzyl 6-O-[2-(4-hydroxy-3-phenylmethoxyphenyl)-4-oxochromen-3-yl] hexanedioate 、 benzyl 2,3,4-tri-O-benzyl-1-O-(trichloroacetimidoyl)-α-D-glucopyranuronate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 以22%的产率得到
  参考文献：
  名称：

  [EN] NOVEL FLAVONOID COMPOUNDS AND USES THEREOF
  [FR] NOUVEAUX COMPOSÉS FLAVONOÏDES ET LEURS UTILISATIONS

  摘要：

  本公开提供了以下公式的化合物、外消旋体、对映体、前药和盐：公式（I）。还提供了这些化合物用于治疗缺血和再灌注损伤的用途。进一步的应用包括治疗由细胞凋亡和/或细胞坏死引起的疾病。

  公开号：

  WO2014056038A1
• 作为产物：
  描述：

  2,3,4-tri-O-benzyl-D-glucopyranosideuronic acid benzyl ester 、 三氯乙腈 生成 benzyl 2,3,4-tri-O-benzyl-1-O-(trichloroacetimidoyl)-α-D-glucopyranuronate
  参考文献：
  名称：

  The synthesis of the glucuronide adduct of Trocade™

  摘要：

  The synthetic preparation of the glucuronide adduct of Trocade(TM), a selective inhibitor of the MMP collagenase, is described. This was achieved by preparation of the protected O-glucuronsyl hydroxylamine (9) and subsequent coupling to the available carboxylic acid (7), followed by deprotection. The synthetic material was identical to authentic isolated metabolite, which confirmed that glucuronidation of Trocade(TM) occurs on the oxygen of the hydroxamic acid. (C) 2000 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(00)01556-2

文献信息

• NMR Spectroscopic and Theoretical Chemistry Studies on the Internal Acyl Migration Reactions of the 1-<i>O</i>-Acyl-β-<scp>d</scp>-glucopyranuronate Conjugates of 2-, 3-, and 4-(Trifluoromethyl)benzoic Acids
  作者：Andrew W. Nicholls、Kazuki Akira、John C. Lindon、R. Duncan Farrant、Ian D. Wilson、John Harding、David A. Killick、Jeremy K. Nicholson

  DOI：10.1021/tx960047r

  日期：1996.1.1

  2-TFMBA isomer was also partly attributed to the high degree of steric hindrance of the trifluoromethyl group obstructing attack by the glucuronic acid 2-hydroxy group on the carbonyl carbon to form the ortho-acid ester intermediate. Some calculated molecular orbital properties, namely, dipole moment, energy of the lowest unoccupied molecular orbital (LUMO), LUMO density, and nucleophilic frontier density

  高分辨率19F NMR光谱已用于研究内部酰基迁移和水解2-，3-和4-（三氟甲基）苯甲酸（TFMBA）的合成β-1-O-酰基-D-吡喃葡萄糖酸酯的动力学。在30°C的磷酸盐缓冲溶液中作为药物酯葡糖醛酸苷的模型。对于每个TFMBA异构体，观察到1-O-酰基葡糖醛酸苷的明显的一级降解和2-，3-和4-O-酰基异构体的顺序出现，即α-和β-异构体形式。2-，3-和4-TFMBA 1-O-酰基异构体的总降解速率常数为0.065h-1、0.25h-1和0.52h-1。为了探究这些1-O-酰基葡糖醛酸内酯的β-端基异构体及其β-2-O-酰基异构体的反应性，理论结构和电子参数差异的原因，并使用半经验分子轨道（AM1和PM3）方法计算了假定的原酸酯中间体的两个结构。通过计算原酸酯中间体中CO键的相对键序，可以观察到反应缓慢的2-TFMBA葡糖醛酸苷与反应更快的3-和4-TFMBA葡糖醛酸苷之间的区别。2-
• Synthesis of benzyl protected β-d-GlcA-(1→2)-α-d-Man thioglycoside building blocks for construction of Cryptococcus neoformans capsular polysaccharide structures
  作者：Lorenzo Guazzelli、Rebecca Ulc、Stefan Oscarson

  DOI：10.1016/j.carres.2014.01.022

  日期：2014.5

  In a project targeting the synthesis of large oligosaccharide structures corresponding to the Cryptococcus neoformans GXM capsular polysaccharide, an easy access to thiodisaccharide building blocks comprising a beta-linked glucuronic acid moiety and a 6-O-acetyl group was required. Several pathways to such building blocks have been investigated, addressing the problem of constructing a beta-linked glucuronic acid residue protected with groups that are orthogonal to a primary acetyl group. Two efficient routes have been developed, one using benzoylated glucosyl donors to form the beta-linkage followed by a change of protecting groups to benzyls and subsequent introduction of the carboxyl function and the acetyl group. The second route explored the possibility to achieve beta-selectivity using glucuronyl donors without acyl protecting groups. BF3- etherate promoted glycosylations with benzyl (2,3,4-tri-O-benzyl-alpha-D-glucupyranosyl)uronate trichloroacetimidate in the presence of nitrile solvents and at low temperatures reproducibly gave good yields of disaccharides with high beta-selectivity. Furthermore, the use of recently reported glucuronyl thioglycoside donors protected with a cyclic 2,4-silylene acetal was found to represent another efficient and completely beta-selective way to desired disaccharide building blocks. (C) 2014 Elsevier Ltd. All rights reserved.