methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-α-D-gluco-hexodialdopyranoside (1,5) | 183170-36-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-α-D-gluco-hexodialdopyranoside (1,5)
• 英文别名: (2S,3S,4S,5R,6S)-6-methoxy-3,4-bis[(4-methoxyphenyl)methoxy]-5-phenylmethoxyoxane-2-carbaldehyde
• CAS: 183170-36-7
• 化学式: C₃₀H₃₄O₈
• 分子量: 522.595
• InChiKey: MMEDWRDKGXMIHR-RLXMVLCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  38
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-α-D-gluco-hexodialdopyranoside (1,5) 在 盐酸 、 正丁基锂 、 zirconocene dichloride 、 三氟化硼乙醚 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 7.5h， 生成 (1R,2S,3S,4R,5R)-3-(benzyloxy)-1,2,4-trihydroxy-5-vinylcyclopentane
  参考文献：
  名称：

  Chiral Cyclopentane-Based Mimics of d-myo-Inositol 1,4,5-Trisphosphate from d-Glucose

  摘要：

  Two routes from D-glucose to chiral, ring-contracted analogs of the second messenger D-myo-inositol 1,4,5-trisphosphate are described. Methyl alpha-D-glucopyranoside was converted by an improved procedure into methyl 4,6-O-(p-methoxybenzylidene)-alpha-D-glucopyranoside (6) and thence into methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-alpha-D-gluco-hexodialdopyranoside (1,5) (14) in four steps. In the first ring-contraction method 14 was converted into methyl 2-O-benzyl-6,7-dideoxy-3,4-bis-O-(p-methoxybenzyl)-alpha-D-gluco-hept-6-enopyranoside (1,5) (15), which on sequential treatment with Cp(2)Zr(n-Bu)(2) followed by BF3 . Et(2)O afforded a mixture of (1R,2S,3S,4R,5S)-3-(benzyloxy)-4-hydroxy-1,2-bis[(p-methoxybenzyl)oxy]-5-vinylcyclopentane (16) and its 4S,5R diastereoisomer 17. Removal of the p-methoxybenzyl groups of 16 and subsequent phosphorylation and deprotection afforded the first target compound, (1R,2R,3S,4R,5S)-3-hydroxy-1,2,4-tris(phosphonooxy)-5-vinylcyclopentane (3). In the second route, intermediate 14 was subjected to SmI2-mediated ring contraction to give (1R,2S,3S,4R,5S)-3-(benzyloxy)-4-hydroxy-5-(hydroxymethyl)-1,2-bis[(p-methoxybenzy)oxy]cyclopentane (20). Benzylation of 20 provided (1R,2S,3S,4R,5S)-3-(benzyloxy)-6-[(benzloxy)methyl]-4-hydroxy-1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (22) and (1R,2S,3S,4R,5S)-3,4-bis(benzyloxy)-5-(hydroxymethyl)- 1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (21), which were elaborated to the target trisphosphates (LR,2R,3S,4R,5S)-3-hydroxy-5-(hydroxymethyl)-1,2,4-tris(phosphonooxy)cyclopentane (4) and (1R,2S,3R,4R,5S)-1,2-dihydroxy-3,4-bis(phosphonooxy)-5-[(phosphonooxy)methyl]cyclopentane (5), respectively. Both 3 and 4 mobilized intracellular Ca2+, but 4 was only a few fold less potent than D-myo-inositol 1,4,5-trisphosphate, demonstrating that effective mimics can be designed that do not bear a six-membered ring.

  DOI：

  10.1021/jo961158y
• 作为产物：
  描述：

  methyl 2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-glucopyranoside 在 lithium aluminium tetrahydride 、 三氯化铝 、 草酰氯 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-α-D-gluco-hexodialdopyranoside (1,5)
  参考文献：
  名称：

  Pentagon IP3: Synthesis of a Ring-Contracted Mimic of a Second Messenger

  摘要：

  DOI：

  10.1021/ja00116a046

文献信息

• Novel Synthesis of Enantiomerically Pure Natural Inositols and Their Diastereoisomers
  作者：Hideyo Takahashi、Hisae Kittaka、Shiro Ikegami

  DOI：10.1021/jo001575h

  日期：2001.4.1

  phosphoinositide signaling system has been discovered in the past 10 years, many factors remain unclear. For this reason, there is an increased demand for supplies of D-myo-inositol and particularly of novel analogues to investigate these biological mechanisms in more detail. Herein, we report the efficient syntheses of all diastereoisomers of inositol starting with 6-O-acetyl-5-enopyranosides. Conversion

  已经发现各种肌醇多磷酸盐引发许多重要的生物学过程。尽管在过去的十年中已经发现了这种磷酸肌醇信号系统的知识，但许多因素仍不清楚。由于这个原因，对D-肌醇特别是新颖类似物的供应的需求增加，以更详细地研究这些生物学机制。在此，我们报告了从6-O-乙酰基-5-烯吡喃糖苷开始的肌醇所有非对映异构体的高效合成。发现用催化量的二氯化钯可以有效地进行6-O-乙酰基-5-烯吡喃糖苷到相应的取代的环己酮的转化（费里尔-II重排）。所获得的β-羟基酮的立体选择性还原提供了所有肌醇非对映异构体的前体，具有良好至优异的产率以及高的立体选择性。这些对映体纯的肌醇非对映异构体的良好可及性导致D-肌醇1,4,5-三磷酸和D-肌醇1,3,4,5-四磷酸的有效合成。
• Chiral Cyclopentane-Based Mimics of <scp>d</scp>-<i>myo</i>-Inositol 1,4,5-Trisphosphate from <scp>d</scp>-Glucose
  作者：David J. Jenkins、Andrew M. Riley、Barry V. L. Potter

  DOI：10.1021/jo961158y

  日期：1996.1.1

  Two routes from D-glucose to chiral, ring-contracted analogs of the second messenger D-myo-inositol 1,4,5-trisphosphate are described. Methyl alpha-D-glucopyranoside was converted by an improved procedure into methyl 4,6-O-(p-methoxybenzylidene)-alpha-D-glucopyranoside (6) and thence into methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-alpha-D-gluco-hexodialdopyranoside (1,5) (14) in four steps. In the first ring-contraction method 14 was converted into methyl 2-O-benzyl-6,7-dideoxy-3,4-bis-O-(p-methoxybenzyl)-alpha-D-gluco-hept-6-enopyranoside (1,5) (15), which on sequential treatment with Cp(2)Zr(n-Bu)(2) followed by BF3 . Et(2)O afforded a mixture of (1R,2S,3S,4R,5S)-3-(benzyloxy)-4-hydroxy-1,2-bis[(p-methoxybenzyl)oxy]-5-vinylcyclopentane (16) and its 4S,5R diastereoisomer 17. Removal of the p-methoxybenzyl groups of 16 and subsequent phosphorylation and deprotection afforded the first target compound, (1R,2R,3S,4R,5S)-3-hydroxy-1,2,4-tris(phosphonooxy)-5-vinylcyclopentane (3). In the second route, intermediate 14 was subjected to SmI2-mediated ring contraction to give (1R,2S,3S,4R,5S)-3-(benzyloxy)-4-hydroxy-5-(hydroxymethyl)-1,2-bis[(p-methoxybenzy)oxy]cyclopentane (20). Benzylation of 20 provided (1R,2S,3S,4R,5S)-3-(benzyloxy)-6-[(benzloxy)methyl]-4-hydroxy-1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (22) and (1R,2S,3S,4R,5S)-3,4-bis(benzyloxy)-5-(hydroxymethyl)- 1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (21), which were elaborated to the target trisphosphates (LR,2R,3S,4R,5S)-3-hydroxy-5-(hydroxymethyl)-1,2,4-tris(phosphonooxy)cyclopentane (4) and (1R,2S,3R,4R,5S)-1,2-dihydroxy-3,4-bis(phosphonooxy)-5-[(phosphonooxy)methyl]cyclopentane (5), respectively. Both 3 and 4 mobilized intracellular Ca2+, but 4 was only a few fold less potent than D-myo-inositol 1,4,5-trisphosphate, demonstrating that effective mimics can be designed that do not bear a six-membered ring.
• Pentagon IP3: Synthesis of a Ring-Contracted Mimic of a Second Messenger
  作者：Andrew M. Riley、David J. Jenkins、Barry V. L. Potter

  DOI：10.1021/ja00116a046

  日期：1995.3