1,2-dideoxy-3,4-di-O-benzyl-6-O-(tert-butyldimethylsilyl)-D-liso-hex-1-enopyranoside | 136656-50-3

• 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: 1,2-dideoxy-3,4-di-O-benzyl-6-O-(tert-butyldimethylsilyl)-D-liso-hex-1-enopyranoside
• 英文别名: 1,5-anhydro-3,4-di-O-benzyl-6-O-t-butyldimethylsilyl-2-deoxy-D-lyxo-hex-1-enitol；3,4-di-O-benzyl-6-O-tert-butyldimethylsilyl-D-galactal；(2R,3R,4R)-((3,4-bis(benzyloxy)-3,4-dihydro-2H-pyran-2-yl)-methoxy)(tert-butyl)dimethylsilane；3,4-di-O-benzyl-6-O-tert-butyl-dimethylsily-D-galactal；[(2R,3R,4R)-3,4-bis(phenylmethoxy)-3,4-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 136656-50-3
• 化学式: C₂₆H₃₆O₄Si
• 分子量: 440.655
• InChiKey: UZVUBPLFXJQAEY-UBFVSLLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.09
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-dideoxy-3,4-di-O-benzyl-6-O-(tert-butyldimethylsilyl)-D-liso-hex-1-enopyranoside 在 2,2,6,6-四甲基哌啶氧化物 、 碘苯二乙酸 、 20% palladium hydroxide-activated charcoal 、 bis(4-fluorophenyl)borinic acid 、 四丁基氟化铵 、 水 、 氢气 、 二甲基二环氧乙烷 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 59.67h， 生成 GSL-1A'
  参考文献：
  名称：

  1,2-顺式-α-立体选择性糖基化利用糖基受体衍生的硼酸酯及其在天然糖鞘脂全合成中的应用

  摘要：

  在糖基受体衍生的硼酸酯存在下，使用1，2-脱水葡萄糖供体和单醇受体进行1，2-顺-α-立体选择性糖基化。反应在温和条件下平稳进行，以中等至高产率提供具有高立体选择性的相应α-糖苷。另外，本方法成功地应用于保护的神经酰胺受体的直接糖基化和天然糖鞘脂（GSL）的总合成。

  DOI：

  10.1021/acs.orglett.6b02488
• 作为产物：
  描述：

  D-三乙酰半乳糖烯 在 咪唑 、 甲醇 、 sodium 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.67h， 生成 1,2-dideoxy-3,4-di-O-benzyl-6-O-(tert-butyldimethylsilyl)-D-liso-hex-1-enopyranoside
  参考文献：
  名称：

  Syntheses of the methyl glycosides of the repeating units of chondroitin 4- and 6-sulfate

  摘要：

  3,4,6-Tri-O-acetyl-D-galactal was transformed into methyl 6-O-acetyl-2-azido-4-O-benzyl-2-deoxy-beta-D-galactopyranoside and its 4-O-acetyl-6-O-benzyl analogue, each of which was glycosylated with activated, O-acetylated derivatives of methyl D-glucopyranosyluronate. The resulting beta-(1----3)-linked disaccharide derivatives were each reductively N-acetylated, hydrogenolysed, O-sulfated, and saponified to afford the disodium salts of methyl 2-acetamido-2-deoxy-3-O-(beta-D-glucopyranosyluronic acid)-4-O-sulfo-beta-D-galactopyranoside and the 6-O-sulfo analogue. D-Galactal was also transformed into activated derivatives of 2-azido-3,6-di-O-benzyl-2-deoxy-D-galactopyranose and their 3,4-di-O-benzyl analogues with various substituents at O-4 and O-6. These glycosyl donors were condensed with 6-O-protected derivatives of methyl 2,3-di-O-benzyl-beta-D-glucopyranoside to give the beta-(1----4)-linked disaccharide derivatives, which were selectively deprotected, then oxidised at C-6 of the gluco unit, reductively N-acetylated, selectively deprotected, O-sulfated at C-4 or C-6 of the galacto unit, and hydrogenolysed to give the disodium salts of methyl 4-O-(2-acetamido-2-deoxy-4-O-sulfo-beta-D-galactopyranosyl)-beta-D- glucopyranosiduronic acid and the 6-O-sulfo analogue.

  DOI：

  10.1016/0008-6215(90)84259-w

文献信息

• Stereoselective Electro‐2‐deoxyglycosylation from Glycals
  作者：Miao Liu、Kai‐Meng Liu、De‐Cai Xiong、Hanyu Zhang、Tian Li、Bohan Li、Xianjin Qin、Jinhe Bai、Xin‐Shan Ye

  DOI：10.1002/anie.202006115

  日期：2020.8.24

  report a novel and highly stereoselective electro‐2‐deoxyglycosylation from glycals. This method features excellent stereoselectivity, scope, and functional‐group tolerance. This process can also be applied to the modification of a wide range of natural products and drugs. Furthermore, a scalable synthesis of glycosylated podophyllotoxin and a one‐pot trisaccharide synthesis through iterative electroglycosylations

  我们报道了一种来自糖基的新型且高度立体选择性的电-2-脱氧糖基化反应。该方法具有出色的立体选择性，范围和功能组公差。该方法也可以用于多种天然产物和药物的改性。此外，还实现了糖基鬼臼毒素的可扩展合成和通过迭代电糖基化的单锅三糖合成。
• Synthesis and Biological Evaluation of α-Galactosylceramide Analogues with Heteroaromatic Rings and Varying Positions of a Phenyl Group in the Sphingosine Backbone
  作者：Yongju Kim、Keunhee Oh、Heebum Song、Dong-Sup Lee、Seung Bum Park

  DOI：10.1021/jm400949h

  日期：2013.9.12

  We designed and synthesized seven α-GalCer analogues with a pyrazole moiety and varying positions of a phenyl group in the sphingosine backbone to polarize cytokine secretion. On the basis of in vitro and in vivo biological evaluations, we found that analogue 5 induced greater polarization toward Th2 and greater secretion of the immunomodulatory cytokine, IL-4, over secretion of pro-inflammatory cytokines

  我们设计并合成了7个具有吡唑部分和鞘氨醇主链中苯基位置不同的α-GalCer类似物，以极化细胞因子的分泌。在体外和体内生物学评估的基础上，我们发现类似物5与促炎性细胞因子IFN-γ和IL-17的分泌相比，诱导了向Th2的更大极化和免疫调节细胞因子IL-4的更大分泌。类似物的单剂量的治疗5个在中枢神经系统的炎性脱髓鞘疾病的动物模型中改善显着疾病的发病机制，相比于KRN7000（的1）。因此，这种新的α-GalCer类似物5 是一种新型的iNKT配体，可刺激抗炎细胞因子的选择性分泌，并通过减少Th1和Th17反应来调节自身免疫性疾病。
• Conversion of Glycals to 1-Azido-2-iodo Sugars Using <i>N</i>-Iodosuccinimide/Sodium­ Azide or Potassium Iodide/Oxone Reagent Systems: Application in the Synthesis of Methyl <i>N</i>-Acetyl-α-<scp>d</scp>-lividosaminide
  作者：Yashwant Vankar、Girish Rawal、Shikha Rani、K. Madhusudanan

  DOI：10.1055/s-2006-958943

  日期：2007.1

  Glycals are readily converted into the corresponding 2-deoxy-2-iodoglycosyl azides, in good to excellent yields in a short time, upon treatment with N-iodosuccinimide/sodium azide or potassium iodide/Oxone reagent systems. One of these 1-azido-2-iodo sugars was converted into methyl N-acetyl-a-d-lividosaminide.

  在用 N-碘代琥珀酰亚胺/叠氮化钠或碘化钾/Oxone 试剂系统处理后，糖醇很容易转化为相应的 2-脱氧-2-碘糖基叠氮化物，并在短时间内以良好至极好的收率。这些 1-azido-2-iodo 糖中的一种被转化为甲基 N-乙酰-ad-lividosaminide。
• TEMPO-Catalyzed Oxidation of 3-<i>O</i>-Benzylated/Silylated Glycals to the Corresponding Enones Using a PIFA–Water Reagent System
  作者：Ande Chennaiah、Ashish Kumar Verma、Yashwant D. Vankar

  DOI：10.1021/acs.joc.8b01191

  日期：2018.9.7

  A simple, highly efficient and regiospecific method for the direct conversion of 3-O-benzylated as well as silylated glycals into the corresponding enones has been developed using PIFA–TEMPO and water reagent system. The reaction is scalable on a gram scale under mild conditions with a yield up to 86%.

  使用PIFA–TEMPO和水试剂系统，已经开发出一种简单，高效且具有区域特异性的方法，可将3- O-苄基化和甲硅烷基化的糖类直接转化为相应的烯酮。在温和条件下，该反应可扩展至克级，收率高达86％。
• Trimethylsilylnitrate−Trimethylsilyl Azide:  A Novel Reagent System for the Synthesis of 2-Deoxyglycosyl Azides from Glycals. Application in the Synthesis of 2-Deoxy-β-<i>N</i>-glycopeptides
  作者：B. Gopal Reddy、K. P. Madhusudanan、Yashwant D. Vankar

  DOI：10.1021/jo0354948

  日期：2004.4.1

  1-azido 2-deoxy sugars in one step in fair to good yields. Galactals offer higher stereoselectivities than do the glucals. Reduction of the azide group with Ph3P−H2O to amino functionality followed by coupling with amino acids leads to the synthesis of novel 2-deoxy-β-N-glycopeptides irrespective of the geometry of initial azido sugars. Using this protocol, a new γ-sugar amino acid derivative is also procured

  包含Me 3 SiN 3和20mol％的Me 3 SiONO 2的新型试剂系统允许在一个步骤中将糖类转化为1-叠氮基2-脱氧糖，以公平至良好的产率。与葡萄糖相比，半乳糖具有更高的立体选择性。与初始叠氮糖的几何结构无关，用Ph 3 P-H 2 O将叠氮化物基团还原为氨基官能团，然后与氨基酸偶联可导致合成新型2-脱氧-β - N-糖肽。使用该协议，还可以购买新的γ-糖氨基酸衍生物。