(±)-1-O-benzyl-2,3:5,6-di-O-isopropylidene-myo-inositol | 58706-24-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (±)-1-O-benzyl-2,3:5,6-di-O-isopropylidene-myo-inositol
• 英文别名: (±)-2,3:5,6-di-O-isopropylidene-1-O-benzyl-myo-inositol；(±)-3-O-benzyl-1,2:4,5-di-O-isopropylidene-myo-inositol；(+/-)-1-O-benzyl-2,3:5,6-di-O-isopropylidene-myo-inositol；(+/-)-3-O-benzyl-1,2:4,5-di-O-isopropylidene-myo-inositol；1-O-benzyl-2,3:5,6-di-O-isopropylidene-myo-inositol；3-O-benzyl-1,2:4,5-di-O-isopropylidene-myo-inositol；(3aS,4S,4aR,7aR,8S,8aR)-8-Benzyloxy-2,2,6,6-tetramethyl-hexahydro-benzo[1,2-d;4,5-d']bis[1,3]dioxol-4-ol
• CAS: 58706-24-4；58769-25-8；98974-91-5；111466-16-1
• 化学式: C₁₉H₂₆O₆
• 分子量: 350.412
• InChiKey: KWQJPCFJDMBLIR-WBAHDQRJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.99
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (±)-1-O-benzyl-2,3:5,6-di-O-isopropylidene-myo-inositol 在 palladium on activated charcoal 吡啶 、 盐酸 、 四丁基溴化铵 、 sodium hydride 、 二正丁基氧化锡 、 对甲苯磺酸 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 22.5h， 生成
  参考文献：
  名称：

  The synthesis and resolution of (±)-1,5,6-tri-O-benzyl-myo-inositol

  摘要：

  Racemic 1,5,6-tri-O-benzyl-myo-inositol was prepared by five routes and converted into 1,5,6-tri-O-benzyl-2,3-O-isopropylidene-myo-inositol, the camphanates of which were readily separated by chromatography. The absolute configurations of the chiral derivatives were established by their conversion into the known chiral 1,4,5,6-tetra-O-benzyl-myo-inositols. 1D-1,5,6-Tri-O-benzyl-2,3-O-isopropylidene-myo-inositol was converted into 1D-1,3,5,6-tetra-O-benzyl-myo-inositol and thence into 1D-2,4-di-O-methyl-myo-inositol. 1D-1,5,6-Tri-O-benzyl-myo-inositol was converted into 1D-1,2,5,6-tetra-O-benzyl-myo-inositol, the diacetate of which is a chiral analogue of "thermosalient crystals". The potential of the above compounds for the synthesis of natural products is surveyed.

  DOI：

  10.1016/0008-6215(90)80132-m
• 作为产物：
  描述：

  Inositol 在 sodium hydride 、 对甲苯磺酸 、 三乙胺 作用下， 以 乙醇 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 5.5h， 生成 (±)-1-O-benzyl-2,3:5,6-di-O-isopropylidene-myo-inositol
  参考文献：
  名称：

  Synthesis and in vitro anticancer activity evaluation of novel bioreversible phosphate inositol derivatives

  摘要：

  The chemistry and biology of phosphorylated inositols have become intense areas of research during the last two decades due to their involvement in various cellular signaling processes. However, the metabolic instability by phosphatases or kinases and poor penetration make it difficult to become a drug used in the clinic. The bioreversible protection technique can enhance membrane penetration characteristics and increase the stability of phosphorylated inositols against enzymatic degradation and is applied widely in drug discovery and development. In this paper, we described the design and synthesis of 22 bioreversible phosphotriester inositols, along with the initial antitumor activity results. Most compounds exhibited significant cytotoxic activity against human cancer cell lines A549, MDA-MB-231 and HeLa, but lower cellular toxicity on normal cell MCF10A in comparison with Cisplatin. These compounds can be used as probes to study the mechanism of intracellular signal transduction mediated by phosphate inositol or as leads of phosphate inositol drugs in the clinic. (C) 2015 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2015.01.064

文献信息

• Resolution of Orthogonally Protected <i>myo</i>-Inositols with Novozym 435 Providing an Enantioconvergent Pathway to Ac₂PIM₁
  作者：Alastair M. M. Lee、Gavin F. Painter、Benjamin J. Compton、David S. Larsen

  DOI：10.1021/jo5019188

  日期：2014.11.21

  4-dimethoxyphenyl)benzyl, propyl, and propargyl protection at O-6 in combination with either allyl or benzyl groups at O-3. Bulky protecting groups slow the rate of acetylation. No reaction was observed for 3,6-di-O-triisopropylsilyl-1,2-O-isopropylidene-myo-inositol. The utility of this methodology was demonstrated by the first reported synthesis of an Ac2PIM1 (9), which used both enantiomers of the resolved

  正交保护的手性肌肉肌醇衍生物是更高阶的重要中间体肌醇含肌醇化合物。这里，通过使用固定化酶的Novozym 435以有效地催化5的乙酰化- [R的外消旋1,2-构成的对映体直径：异亚丙基肌醇-inositols在O-3和O-6是化学上和空间上具有多样的保护基团描述。烯丙基，苄基，4-溴-，4-甲氧基-，4-硝基和4-（3,4-二甲氧基苯基）苄基，丙基和炔丙基在O-6的保护下与任何一个烯丙基结合均能成功解决拆分问题或O-3处的苄基。庞大的保护基团会降低乙酰化速度。3,6-di-未观察到反应Ø -triisopropylsilyl -1,2- Ø异亚丙基肌醇肌醇。该方法的实用性通过首次报道的Ac 2 PIM 1（9）合成得到证明，该化合物使用了拆分后的3- O-烯丙基-6- O-苄基-1,2- O-异亚丙基-肌醇的两种对映体。-肌醇的融合合成。
• Improved preparation of acetals of myo-inositol and its (±)-1-benzyl ether: conformational analysis of di-O-isopropylidene-myo-inositol derivatives
  作者：Roberto Fernandez de la Pradilla、Carlos Jaramillo、Jesus Jimenez-Barbero、Manuel Martin-Lomas、Soledad Penades、Amparo Zapata

  DOI：10.1016/0008-6215(90)84052-v

  日期：1990.10

  myo -inositol with 3–5 equiv. of 2-methoxypropene or 2,2-dimethoxypropane in methyl sulfoxide or N,N -dimethylformamide gave mixtures of the 1,2:4,5-, 1,2:5,6-, and 1,2:3,4-di- O -isopropylidene derivatives with little or none of the 1,2:3,4:5,6-triacetal 5 . With ≈ 7 equiv. of 2-methoxypropene in methyl sulfoxide-hexane, 70% of 5 was obtained. Kinetic acetonation of 1- O -benzyl- myo -inositol gave

  摘要肌醇与3-5当量的酸催化反应。将2-甲氧基丙烯或2,2-二甲氧基丙烷在甲基亚砜或N，N-二甲基甲酰胺中得到1,2,4,5-，1,2：5,6-和1,2：3,4-的混合物几乎没有或没有1,2：3,4：5,6-三缩醛5的二-O-异亚丙基衍生物。≈7当量 在甲基亚砜-己烷中得到2-甲氧基丙烯，得到5的70％。1-O-苄基-肌醇的动力学丙酮化主要产生3,4：5,6-二缩醛，而热力学条件主要产生2,3：5,6-二缩醛。1-O-苄基-2,3：4,5-二-O-异亚丙基-肌醇是次要产品，主要存在于非极性溶剂的椅子构型和极性偏斜的船形结构中。溶剂，而6-乙酸盐仅采用斜舟构象。
• Regioselective functionalizations and conformational studies of di-O-isopropylidene-myo-inositol derivatives
  作者：Sung-Kee Chung、Youngha Ryu

  DOI：10.1016/0008-6215(94)84082-2

  日期：1994.5

  in IR and 1H NMR spectra, and the HO-3 group was identified as the hydrogen-bonding donor in 5 and 6. In their crystalline states, diol 5 prefers a chair conformation and diol 6 a twist boat (skew) conformation. Both compounds appear to have substantial populations of chair conformations in the gas and solution phases, on the basis of the MM-2 energy minimizations and comparisons of vicinal coupling

  摘要（±）-1,2：4,5-二-O-异亚丙基-肌醇（5）和（±）-1,2：5,6-二-O-异亚丙基-肌醇（6）在特定条件下，在HO-3上的烷基化，酰化和甲硅烷基化反应分别优先于HO-6和HO-4进行区域选择性功能化。分子内氢键的存在在IR和1H NMR光谱中是明显的，并且HO-3基团被鉴定为5和6中的氢键供体。在它们的结晶态中，二醇5更喜欢椅子构型，而二醇6更喜欢扭曲。船（偏斜）构象。两种化合物在气相和溶液相中似乎都具有大量的椅子构象，基于MM-2的能量最小化和在1H NMR光谱（在CDCl3和Me2SO-d6中）观察到的邻位耦合常数的比较，并根据晶体和MM-2构型进行计算。建议作为观察到的选择性的解释，HO-3基团的动力学酸性可通过其与顺式-邻位氧的分子内氢键结合而增强，或3-醇盐的亲核性可由于其相互作用而增强。与顺式邻位氧作用相似，其作用方式类似于贯穿空间的α效应。
• Bio-inspired synthesis of rare and unnatural carbohydrates and cyclitols through strain driven epimerization
  作者：Raja Mohanrao、Aromal Asokan、Kana M. Sureshan

  DOI：10.1039/c4cc00868e

  日期：——

  Bio-inspired isomerization of carbohydrates and cyclitols to their rare and unnatural isomers, through strain-driven epimerization of trans-ketals to cis-ketals, is introduced.

  通过通过对碳水化合物和环己醇进行仿生异构化，通过应变驱动的将反式-酮缩醛异构化为顺式-酮缩醛，引入了它们罕见且非自然的异构体。
• Gigg, Jill; Gigg, Roy; Payne, Sheila, Journal of the Chemical Society. Perkin transactions I, 1987, p. 423 - 430
  作者：Gigg, Jill、Gigg, Roy、Payne, Sheila、Conant, Robert

  DOI：——

  日期：——