3,4,6-tri-O-benzyl-2-C-acetoxymethylgalactal | 153081-97-1

• 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: 3,4,6-tri-O-benzyl-2-C-acetoxymethylgalactal
• 英文别名: [(2R,3R,4R)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-5-yl]methyl acetate
• CAS: 153081-97-1
• 化学式: C₃₀H₃₂O₆
• 分子量: 488.58
• InChiKey: RCZNWJHFFDDOJO-OCBJUFRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  36
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-2-C-acetoxymethylgalactal 在 吡啶 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  蒙脱土K-10黏土催化2-C-羟甲基-d-糖，3,4,6-三-O-烷基-d-糖和3,4-（二氢-2H-吡喃-5-的Ferer重排yl）甲醇：一些意料之外的多米诺骨牌转化。

  摘要：

  蒙脱石K-10粘土催化的3,4,6-三-O-烷基-2-C-羟甲基-d-糖基，3,4,6-三-O-乙酰基-d-糖基，3，描述了4,6-三-O-烷基-d-糖和3,4-（二氢-2H-吡喃-5-基）甲醇与少量醇和酚。2-C-羟甲基-d-缩醛与酚的反应类似于2-C-乙酰氧基甲基-d-缩醛的反应，得到吡喃并[2,3-b]苯并吡喃。这种蒙脱土K-10粘土催化的转化在环境（方法1）和微波条件（方法2）下都很容易。3,4-（二氢-2H-吡喃-5-基）甲醇与对甲酚，2,6-二甲苯酚和乙醇的重排反应导致完全出乎意料的转化。在蒙脱石K-10存在下，2-C-羟甲基-d-半乳糖与2,6-二甲基苯酚的反应导致了新的多米诺骨牌转化，提供了4-（5'，6' -二氢-4H-吡喃-3′-基甲基）-2，6-二甲基苯酚。相比之下，3,4,6-三-O-乙酰基-d-葡糖醇提供了Ferrier重排产物，即2,6-二甲基苯基4,6-二-O-乙酰基-2

  DOI：

  10.1016/j.carres.2011.03.027
• 作为产物：
  描述：

  (2R,3R,4R)-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-dihydro-2H-pyran-5-carbaldehyde 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 3,4,6-tri-O-benzyl-2-C-acetoxymethylgalactal
  参考文献：
  名称：

  A new ferrier system: 2-C-acetoxymethylglycals. A covenient entry to 2-C-methylene glycosides

  摘要：

  介绍了三-O-苄基-2-C-乙酰氧甲基苷的合成及随后的费里尔重排反应生成 2-C-亚甲基苷的过程。

  DOI：

  10.1039/c39930001394

文献信息

• HSAB-driven regioselectivity difference in the Lewis-acid catalyzed reactions of 2-C-substituted glycals with sulfur and oxygen nucleophiles: direct versus allylic substitution
  作者：Paramathevar Nagaraj、Namakkal G. Ramesh

  DOI：10.1016/j.tet.2011.09.122

  日期：2011.12

  2-C-acteoxymethyl glycals with thiophenols and phenols has been observed. The reaction with thiophenols led to preferential formation of a new class of compounds viz. 2-C-arylthiomethyl glycals via direct attack at the C-2 side chain primary carbon bearing the leaving group. In contrast, phenols were reported to afford predominantly 2-C-methylene-O-aryl glycosides via allylic attack at the anomeric

  在路易斯酸催化的2 - C-乙氧基甲基甲基糖与硫酚和苯酚的反应中，观察到了显着的区域选择性差异。与硫酚的反应导致优先形成新型化合物，即。通过直接攻击带有离去基团的C -2侧链伯碳的2- C-芳基硫基甲基糖。相反，据报道苯酚主要提供2- C-亚甲基-O-芳基糖苷通过对异头碳的烯丙基攻击。观察到的结果与先前针对类似类型的简单糖类反应提出的HSAB原理很好地相关。另外，还报道了在过量苯硫酚存在下形成不寻常的双硫代芳基化产物。
• Gold(III) Chloride and Phenylacetylene: A Catalyst System for the Ferrier Rearrangement, and<i>O</i>-Glycosylation of 1-<i>O</i>-Acetyl Sugars as Glycosyl Donors
  作者：Rashmi Roy、Parasuraman Rajasekaran、Asadulla Mallick、Yashwant D. Vankar

  DOI：10.1002/ejoc.201402606

  日期：2014.9

  have developed a new catalyst system comprising AuCl3 and phenylacetylene that promotes the Ferrier rearrangement of glycals and 2-acetoxymethylglycals with different nucleophiles, and also the O-glycosylation of 1-O-acetyl sugars to obtain a variety of useful glycosides at room temperature through relay catalysis. Good anomeric selectivity was observed for the Ferrier rearrangements, whereas the O-glycosylation

  我们开发了一种新的催化剂体系，包含 AuCl3 和苯乙炔，可促进具有不同亲核试剂的糖类和 2-乙酰氧基甲基糖类的费里尔重排，以及 1-O-乙酰糖的 O-糖基化，以通过以下方式在室温下获得各种有用的糖苷中继催化。对于 Ferrier 重排观察到良好的异头异构体选择性，而 1-O-乙酰糖的 O-糖基化产生具有中等至极好选择性的非对映异构体混合物。
• Synthesis of C-2 Methylene O- and C-Glycosides and Sugar Derived α-Methylene-δ-valerolactones from C-2-Acetoxymethyl Glycals
  作者：Anuradha Gupta、Yashwant D. Vankar

  DOI：10.1016/s0040-4020(00)00775-4

  日期：2000.10

  C-2-Methylene O- and C-glycosides are readily synthesized from C-2-acetoxymethyl glycals using Nafion-H(R), montmorillonite K-10, LiClO4 (0.07 M) in dichloromethane and Pd(PPh3)(4) as catalysts. Exclusive alpha or beta selectivities have been observed with various primary, secondary and tertiary alcohols, phenols and diethyl malonate. Further, C-2-acetoxymethyl glycals are also converted into corresponding alpha -methylene-delta -valerolactones in good yields in one step using m-CPBA in the presence of BF3. Et2O. (C) 2000 Elsevier Science Ltd. All rights reserved.
• SN2 substitution reaction of 2-C-acetoxymethyl glycals catalyzed by iodine: a novel synthesis of 2-C-N-arylamidomethyl glycals
  作者：J.S. Yadav、G. Narasimhulu、N. Umadevi、Y. Vikram Reddy、B.V. Subba Reddy

  DOI：10.1016/j.tetlet.2012.11.106

  日期：2013.2

  The reaction of 2-C-acetoxymethyl glycals with N-aryl amides such as N-aryltosyl amine, p-toluenesulfonamide, and t-butoxycarbonyl amine in the presence of a catalytic amount of iodine affords a novel class of 2-C-N-arylamidomethyl glycals through direct attack at the C-2 position bearing the acetyl group under mild reaction conditions. The use of iodine makes this method simple, convenient, and cost-effective. This is the first report on nucleophilic substitution of 2-C-acetoxymethyl glycals with N-aryl amides using molecular iodine as a catalyst. (C) 2012 Elsevier Ltd. All rights reserved.
• Tailor-made chiral pyranopyrans based on glucose and galactose and studies on self-assembly of some crystals and low molecular weight organogel (LMOG)
  作者：Soumik Roy、Arijit Chakraborty、Basab Chattopadhyay、Abir Bhattacharya、Alok K. Mukherjee、Rina Ghosh

  DOI：10.1016/j.tet.2010.08.054

  日期：2010.10

  InCl3 catalyzed reactions of 2-C-acetoxymethylglycal derivatives with different phenolic compounds resulted in the formation of sugar based pyranoarenopyrans in good yields and moderate to excellent diastereoselectivity in favor of 10aR- or 12aR- or 14aR-products. One of the synthesized compounds, viz. (2R,3R,12aR)-2,3,5,12a-tetrahydro-2-methoxymethyl-3-methoxypyrano[2,3-b]naphtho[1,2-e]pyran gelated polar solvents like MeOH, EtOH and non-polar solvents like pentane, hexane, heptane, octane, pet. ether, etc. The SEM picture of the corresponding hexane xerogel exhibited a rare type of microtubular gel assembly, whereas the SEM pictures of MeOH and pet. ether xerogels showed different types of three-dimensional network. Study of the MeOH gel by Fluorescence spectroscopy, H-1 NMR and X-ray powder diffraction analysis indicated that the supramolecular assembly in the MeOH gel can be attributed to pi-stacking. The crystal packing of (2R.3R,10aR)-3,10a-dihydro-2-methoxymethyl-3-methoxy-7-methyl-2H,5H-pyrano[2,3-b][1]benzopyran, a benzopyran analogue of the above organogelator was stabilized by C-H center dot center dot center dot O and C-H center dot center dot center dot pi hydrogen bonds forming one-dimensional columns parallel to the [001] direction, whereas the corresponding benzopyran 3-epimer showed only C-H center dot center dot center dot O hydrogen bonds among the molecules. (C) 2010 Elsevier Ltd. All rights reserved.