1,3,4,5-Tetra-O-benzyl-D-myo-inositol | 261722-84-3

• 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: 1,3,4,5-Tetra-O-benzyl-D-myo-inositol
• CAS: 261722-84-3
• 化学式: C₃₄H₃₆O₆
• 分子量: 540.656
• InChiKey: XGMQKZYVODIFBY-ZGSWEVDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.06
• 重原子数：
  40.0
• 可旋转键数：
  12.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  77.38
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,3,4,5-Tetra-O-benzyl-D-myo-inositol 在 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 叔丁基二甲硅基三氟甲磺酸酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.33h， 生成 Benzoic acid (2R,3S,4S,5R,6R)-2-((1R,2S,3R,4R,5S,6S)-3-acetoxy-2,4,5,6-tetrakis-benzyloxy-cyclohexyloxy)-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Targeted Glycosyl Donor Delivery for Site-Selective Glycosylation^,1

  摘要：

  [GRAPHICS]n-Pentenyl ortho esters (NPOEs) and n-pentenyl glycosides (NPGs) are interconvertible glycosyl donors which are activated by reaction with halonium ions. In a series of cyclic syn-1,3-diols, NPOEs have been found to specifically glycosylate the equatorial-OH while the NPG glycosylates predominantly, but not exclusively, the axial-OR. When the cyclic diol acceptor is presented with equivalent amounts of an NPOE and an NPG in a three component reaction, a single, double-glycosylation product is obtained, which conforms to the foregoing preferences, presenting evidence for site-selective glycosylation.

  DOI：

  10.1021/ol0001214
• 作为产物：
  描述：

  (+/-)-3,4-di-O-benzyl-1,2-O-isopropylidene myo-inositol 在 吡啶 、 盐酸 、 sodium hydroxide 、 四丁基溴化铵 、 二正丁基氧化锡 作用下， 以 甲醇 为溶剂， 反应 12.92h， 生成 1,3,4,5-Tetra-O-benzyl-D-myo-inositol
  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

文献信息

• Concerning the reactivities of the C-1, C-2 and C-6 hydroxy groups of myo-inositol
  作者：Gopinadhan nair Anilkumar、Zhaozhong J. Jia、Ralf Kraehmer、Bert Fraser-Reid

  DOI：10.1039/a907318c

  日期：——

  Regioselectivities in the reactions of the three contiguous free hydroxy groups at C-6, C-1, and C-2 of 3,4,5-tri-O-benzyl-D-myo-inositol have been examined. Stannylene activation permits selective alkylation and esterification at C-1; however, acyl migration back and forth between C-1 and C-2 leads to unpredictable ratios of the isolated regioisomers. With the stable C1-alkylated products, further alkylation is regioslective for the axial C-2–OH, whereas acylation is regioselective for the equatorial C-6–OH. In most cases the ‘other’ regioisomer is not observed, the by-products being those of dialkylation or diacylation.

  已对3,4,5-三-O-苄基-D-myo-肌醇在C-6、C-1和C-2的三个相邻游离羟基的反应中的区域选择性进行了研究。锡烯的激活使得在C-1进行选择性烷基化和酯化成为可能；然而，C-1和C-2之间的酰基迁移前后导致所得到的区域异构体比例不可预测。在稳定的C1-烷基化产物中，进一步的烷基化对此轴向的C-2–OH具有区域选择性，而酰基化则对赤道的C-6–OH具有区域选择性。在大多数情况下，‘其他’区域异构体未被观察到，副产物为双烷基化或双酰基化的产物。
• Regioselective Mannosylation Routes to the Antigenic myo-Inositol Component of Mycobacterium tuberculosis
  作者：G. Anilkumar、Mark R. Gilbert、Bert Fraser-Reid

  DOI：10.1016/s0040-4020(00)00156-3

  日期：2000.3

  A differentially protected derivative of myo-inositol with free hydroxyl groups at C6 and C2 is regioselectively mannosylated at C2, and subsequently at C6 with the same or a different donor to give the dimannosylated inositol antigenic core of Mycobacterium tuberculosis. Deacetylation now frees C1 for phosphorylation.

  在C6和C2处具有游离羟基的肌醇的差异保护衍生物在C2处区域选择性地被甘露糖基化，随后在C6处以相同或不同的供体被赋予二分糖基化的肌醇结核分枝杆菌的肌醇抗原核心。现在，脱乙酰基释放C1进行磷酸化。
• Reciprocal donor acceptor selectivity (RDAS): A new concept for "matching" donors with acceptors
  作者：Bert Fraser-Reid、J Cristobal Lopez、K V Radhakrishnan、Mateusz Mach、Urs Schlueter、Ana Gomez、Clara Uriel

  DOI：10.1139/v02-137

  日期：2002.8.1

  Lemieux's extensive work on replacement reactions at the anomeric center helped to establish the fact that the O-2-protecting group of a donor exerts powerful control over stereoselectivity in glycoside coupling reactions. This manuscript shows that the O-2-protecting group of a donor also exerts powerful, indeed sometimes total, control over regioselectivity in glycosidation of diols. The latter acceptors also exhibit preferences over the donor, thereby providing evidence for the concept of reciprocal donor acceptor selectivity (RDAS). The latter concept is put to the test by simultaneously presenting an acceptor diol with equivalent amounts of two donors, in the hope of achieving double differential glycosidation leading to one-pot assembly of a trisaccharide. When the pair of donors did not conform to RDAS principles the reaction did not proceed beyond a dissacharide. However, when the pair was RDAS sanctioned, a single trisaccharide (out of four possibilities) was obtained.Key words: regiocontrolled glycosidation, armed and disarmed donors, di- and trioxolenium ions, oxocarbenium ion.

  Lemieux在异构中心的替代反应方面的广泛研究有助于确立这样一个事实：供体的O-2保护基在糖苷偶联反应中对立体选择性具有强大的控制作用。本文表明，供体的O-2保护基对二醇的糖苷化反应的位置选择性也具有强大的、有时甚至是完全的控制作用。后一种受体对供体也表现出偏好，从而为相互供体受体选择性（RDAS）概念提供了证据。后一概念通过同时将一个受体二醇与等量的两个供体呈现，希望实现双重差异糖苷化，从而实现三糖的一锅法组装。当这对供体不符合RDAS原则时，反应无法超过二糖。然而，当这对供体符合RDAS原则时，获得了一个单一的三糖（四种可能性中的一种）。关键词：位置控制的糖苷化，武装和非武装供体，二和三氧杂环丙阳离子，羰基离子。
• Evidence for Efficient Unpromoted Regioselective Reactions of Vicinal and Non-Vicinal Diols
  作者：B. Fraser-Reid、J. C. Lopez、G. nair Anilkumar、J. C. Lopez、L. G. Nair、A. Gomez、C. Uriel、K. V. Radhakrishnan

  DOI：10.1071/ch01146

  日期：——

  reports that the NPOE and (NPGAC) donors frequently react at only one of the two hydroxy groups in good yield, whereas the corresponding benzylated donor (NPGALK) is less discriminating, and frequently gives lower yields. In a key experiment to examine the basis of the selectivity, it was found that the highly hindered C3 OH of 4,6-O-benzylidene methyl a-D-altropyranoside was selectively glycosylated

  Angyal 实验室 1965 年发表的一篇文章报道说，四氧苄基肌醇的顺式邻位二醇基团与赤道 OH 处的酰化剂发生区域选择性反应，有时仅与酰化剂反应，但与轴向 OH 处的烷化剂反应。Fraser-Reid 及其同事最近的报告表明，对于四-O-苄基肌醇的反式-1,3-二醇以及二-O-烯丙基甘露吡喃糖苷的 C2-C4 羟基也发现了这种选择性. 此外，后者的工作人员报告说区域选择性可以扩展到糖苷化反应。因此，正戊烯基原酸酯 (NPOE) 和 2-O-酰基正戊烯基糖苷 (NPGAC) 供体在赤道 OH 处优先反应（如果不是排他性的），而 2-O-烷基对应物 (NPGALK) 则产生混合物，通常主要糖苷化发生在轴向 OH。本手稿检查了几种邻二醇，并报告说 NPOE 和 (NPGAC) 供体经常仅在两个羟基中的一个上反应，产率很高，而相应的苄基化供体 (NPGALK) 区分度较低，并且经常给出较低的产