D-myo-inositol 1,2,4,5-tetrakisphosphate | 117142-45-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: D-myo-inositol 1,2,4,5-tetrakisphosphate
• 英文别名: Myo-inositol 1,2,4,5-tetrakisphosphate；DL-Myo-inositol 1,2,4,5-tetrakisphosphate
• CAS: 117142-45-7
• 化学式: C₆H₁₆O₁₈P₄
• 分子量: 500.077
• InChiKey: ZAWIXNGTTZTBKV-PCTUYBJVSA-N

物化性质

• 沸点：
  1015.6±75.0 °C(Predicted)
• 密度：
  2.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -3.37
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  307.5
• 氢给体数：
  10.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  D-myo-inositol 1,2,4,5-tetrakisphosphate 在 sodium amide 作用下， 以 1,4-二氧六环 、 氨 为溶剂， 反应 2.0h， 以22%的产率得到L-myo-inositol 1,2,4,6-tetrakisphosphate
  参考文献：
  名称：

  Synthesis of the enantiomers of myo-inositol 1,2,4,5-tetrakisphosphate, a regioisomer of myo-inositol 1,3,4,5-tetrakisphosphate

  摘要：

  本文描述了合成外消旋肌醇1,2,4,5-四磷酸DL-Ins(1,2,4,5)P₄ 5ab及其对映体D-和L-肌醇1,2,4,5-四磷酸5a和5b的路线。对于合成外消旋体5ab，3,6-二-O-苯甲酰基-1,2:4,5-二-O-异亚丙基-肌醇7ab通过两步反应从肌醇制备得到。在酸性条件下水解缩酮得到DL-1,4-二-O-苯甲酰基-肌醇8ab。然后使用氯(二乙氧基)膦在碱存在下对化合物8ab进行膦酸化，随后进行氧化和三步去保护策略，得到DL-Ins(1,2,4,5)P₄ 5ab。手性四磷酸盐5a和5b则通过不同的路线合成。在温和酸性条件下选择性地除去DL-3,6-二-O-苄基-1,2:4,5-二-O-异亚丙基-肌醇13ab的4,5-异亚丙基保护基，得到二醇14ab。在4,5-位进行对甲氧基苄基化，然后酸水解顺式异亚丙基缩酮，得到顺式二醇16ab。在赤道羟基上选择性地与(S)-(+)-O-乙酰基扁桃酸偶联合成，得到两个非对映异构体18和19，通过色谱法分离。单一非对映异构体在碱性条件下水解得到对映体16a和16b。酸性水解得到D-和L-3,6-二-O-苄基-肌醇20a和20b。四醇20a和20b进行膦酸化和氧化得到完全保护的衍生物，然后去保护得到四磷酸盐5a和5b。化合物20a的绝对构型通过化学方法确定。DL-1,2:4,5-二-O-异亚丙基-肌醇12ab与(S)-(+)-O-乙酰基扁桃酸偶联得到双酯混合物26和27，通过非对映异构体混合物的结晶得到纯异构体27。碱性水解得到纯对映体12a（其绝对构型已知），苄基化后酸水解得到四醇20a，其物理性质与先前通过不同路线合成的化合物20a相同。D-Ins(1,2,4,5)P₄ 5a是一种有效的细胞内Ca²⁺离子动员剂，而L-Ins(1,2,4,5)P₄ 5b则无效。

  DOI：

  10.1039/a608337d
• 作为产物：
  描述：

  Phosphoric acid dibenzyl ester (1R,2S,3R,4R,5S,6S)-2,5-bis-benzyloxy-3,4,6-tris-(bis-benzyloxy-phosphoryloxy)-cyclohexyl ester 在 sodium amide 作用下， 以 1,4-二氧六环 、 氨 为溶剂， 反应 2.0h， 以40%的产率得到D-myo-inositol 1,2,4,5-tetrakisphosphate
  参考文献：
  名称：

  Synthesis of the enantiomers of myo-inositol 1,2,4,5-tetrakisphosphate, a regioisomer of myo-inositol 1,3,4,5-tetrakisphosphate

  摘要：

  本文描述了合成外消旋肌醇1,2,4,5-四磷酸DL-Ins(1,2,4,5)P₄ 5ab及其对映体D-和L-肌醇1,2,4,5-四磷酸5a和5b的路线。对于合成外消旋体5ab，3,6-二-O-苯甲酰基-1,2:4,5-二-O-异亚丙基-肌醇7ab通过两步反应从肌醇制备得到。在酸性条件下水解缩酮得到DL-1,4-二-O-苯甲酰基-肌醇8ab。然后使用氯(二乙氧基)膦在碱存在下对化合物8ab进行膦酸化，随后进行氧化和三步去保护策略，得到DL-Ins(1,2,4,5)P₄ 5ab。手性四磷酸盐5a和5b则通过不同的路线合成。在温和酸性条件下选择性地除去DL-3,6-二-O-苄基-1,2:4,5-二-O-异亚丙基-肌醇13ab的4,5-异亚丙基保护基，得到二醇14ab。在4,5-位进行对甲氧基苄基化，然后酸水解顺式异亚丙基缩酮，得到顺式二醇16ab。在赤道羟基上选择性地与(S)-(+)-O-乙酰基扁桃酸偶联合成，得到两个非对映异构体18和19，通过色谱法分离。单一非对映异构体在碱性条件下水解得到对映体16a和16b。酸性水解得到D-和L-3,6-二-O-苄基-肌醇20a和20b。四醇20a和20b进行膦酸化和氧化得到完全保护的衍生物，然后去保护得到四磷酸盐5a和5b。化合物20a的绝对构型通过化学方法确定。DL-1,2:4,5-二-O-异亚丙基-肌醇12ab与(S)-(+)-O-乙酰基扁桃酸偶联得到双酯混合物26和27，通过非对映异构体混合物的结晶得到纯异构体27。碱性水解得到纯对映体12a（其绝对构型已知），苄基化后酸水解得到四醇20a，其物理性质与先前通过不同路线合成的化合物20a相同。D-Ins(1,2,4,5)P₄ 5a是一种有效的细胞内Ca²⁺离子动员剂，而L-Ins(1,2,4,5)P₄ 5b则无效。

  DOI：

  10.1039/a608337d

文献信息

• Total synthesis of myo-inositol polyphosphates from benzene via conduritol B derivatives
  作者：Howard A.J. Carless、Kofi Busia

  DOI：10.1016/s0040-4039(00)97419-7

  日期：1990.1

  The four (±)--inositol phosphates 1,4,5-IP3 (1), 2,4,5-IP3 (15), 1,2,4,5-IP4 (17) and 4,5-IP2 (19) have been synthesised from benzene, using the protected conduritol B (10) as the key intermediate.

  四种（±）--肌醇磷酸酯1,4,5-IP 3（1），2,4,5-IP 3（15），1,2,4,5-IP 4（17）和4,5 -IP 2（19）已经由苯合成，使用被保护的赤豆糖醇B（10）作为关键中间体。
• Flexible Stereo- and Regioselective Synthesis ofmyo-Inositol Phosphates(Part 1): Via Symmetrical Conduritol B Derivatives
  作者：Michael A. L. Podeschwa、Oliver Plettenburg、Hans-Josef Altenbach

  DOI：10.1002/ejoc.200400911

  日期：2005.7

  myo-inositol phosphates. Optically pure compounds can be prepared, in both forms, from p-benzoquinone by enzymatic resolution of a diacetoxyconduritol key intermediate. Monosubstituted inositol derivatives can be obtained by breaking the C2 symmetry of conduritol B derivatives. A wide variety of myo-inositol phosphates can be synthesized by combining the previously reported symmetrical approach with

  描述了用于制备肌醇磷酸酯的实用路线。通过酶促拆分二乙酰氧基硬糖醇关键中间体，可以从对苯醌制备两种形式的光学纯化合物。单取代的肌醇衍生物可以通过破坏 conduritol B 衍生物的 C2 对称性来获得。通过将先前报道的对称方法与这种新的非对称方法相结合，可以合成多种肌醇磷酸酯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Process for the preparation of myoinositol derivatives
  申请人：MITSUI TOATSU CHEMICALS, Inc.

  公开号：EP0262227A1

  公开（公告）日：1988-04-06

  Myoinositol phosphates and salts thereof represented by general formula (I) and process for their preparation. The myoinositol derivatives are prepared by reacting a phosphorylating agent with a myoinositol derivative wherein sites other than those to be substituted by phosphate residues are substituted by a substituent capable of being eliminated by catalytic reduction, and subjecting the product to catalytic reduction.

  由通式(I)表示的肌醇磷酸盐及其盐类以及它们的制备方法。肌醇衍生物的制备方法是将磷酸化剂与肌醇衍生物反应，其中磷酸残基取代的位点以外的位点被能够通过催化还原消除的取代基取代，然后将产物进行催化还原。
• Regiospecific phosphohydrolases from Dictyostelium as tools for the chemoenzymatic synthesis of the enantiomers d-myo-inositol 1,2,4-trisphosphate and d-myo-inositol 2,3,6-trisphosphate: non-physiological, potential analogues of biologically active d-myo-inositol 1,3,4-trisphosphate
  作者：Stephan Adelt、Oliver Plettenburg、Guido Dallmann、Frank P Ritter、Stephen B Shears、Hans-Josef Altenbach、Günter Vogel

  DOI：10.1016/s0960-894x(01)00536-4

  日期：2001.10

  A new de novo synthesis of the enantiomeric pair D-myo-inositol 1,2,4-trisphosphate and D-myo-inositol 2,3,6-trisphosphate is described. Starting from enantiopure dibromocyclohexenediol, several C-2 Symmetrical building blocks were synthesized which gave access to D-myo-inositol 1,2,4,5-tetrakisphosphate and D-Myo-inositol 1,2,3,6-tetrakisphosphate. Exploiting the high regiospecificity of two partially purified phosphohydrolases from Dictyostelium, a 5-phosphatase and a phytase, the inositol tetrakisphosphates were converted enzymatically to the target compounds. Their potential to modulate the activity of Ins(3,4,5,6)P-4 I-kinase was investigated and compared with the effects Of D-myo-inositol 1,3,4-trisphosphate. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Divergent Syntheses of All Possible Optically Active Regioisomers of <i>m</i><i>yo</i>-Inositol Tris- and Tetrakisphosphates
  作者：Sung-Kee Chung、Yong-Uk Kwon、Jung-Han Shin、Young-Tae Chang、Changgook Lee、Boo-Gyo Shin、Kyung-Cheol Kim、Mahn-Joo Kim

  DOI：10.1021/jo0257694

  日期：2002.8.1

  Since the discovery Of D-myo-inositol 1,4,5-trisphosphate, which plays a pivotal role as a second messenger in transmembrane signaling, the scope of the phosphoinositide-based signaling processes has been continually expanding. However, the clear understanding of the molecular signal transduction mechanisms including the functions of newly found IPn is still lacking. As a continuing effort to our previously reported syntheses of all possible 39 optically inactive regioisomers of myoinositol phosphates (IPn; n = 1-6), we synthesized all possible optically active regioisomers of myo-IP3 and myo-IP4 using chiral IBz(3)s and IBz(2)s, respectively. A series of procedures involving CRL-catalyzed enzymatic resolution of racemic 1,2:5,6-di-O-isopropylidene-myo-inositoI and base-catalyzed benzoyl migration in tri- and dibenzoyl-isopropylidene-myo-inositol afforded eight enantiomeric pairs of IBz(3) and six enantiomeric pairs of IBz(2), respectively. Phosphorylation of these intermediates by the phosphitylation and oxidation procedure gave the target products.