2-acetoxymethyl-1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hex-1-enitol | 153153-30-1

• 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: 2-acetoxymethyl-1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hex-1-enitol
• 英文别名: 2-acetoxymethyl- 3,4,6-tri-O-benzyl-D-glucal；3,4,6-tri-O-benzyl-2-C-acetoxymethylglucal；[(2R,3S,4R)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-5-yl]methyl acetate
• CAS: 153153-30-1
• 化学式: C₃₀H₃₂O₆
• 分子量: 488.58
• InChiKey: RCZNWJHFFDDOJO-IDZRBWSNSA-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：

  2-acetoxymethyl-1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hex-1-enitol 在 正丁基锂 、 indium(III) bromide 、 三氟化硼乙醚 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.25h， 生成
  参考文献：
  名称：

  1-C-炔基-2-脱氧-2-C-亚甲基吡喃糖苷衍生的新设计的Ferrier和Ferrier-Nicholas系统的面向多样性的合成努力

  摘要：

  一种新的吡喃糖系统，用于类似费瑞尔的反应，即1 C-炔基-2-脱氧2 C-亚甲基吡喃糖苷，可通过有效的合成途径从市售的三邻乙酰基d葡糖醛中获得。被设计。这些化合物可以转化为其六羰基二钴-炔基类似物，即Ferrier-Nicholas阳离子的现成前体，从而产生具有骨架和功能多样性的衍生物。

  DOI：

  10.1002/ejoc.201801004
• 作为产物：
  描述：

  (2R,3S,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 2-acetoxymethyl-1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hex-1-enitol
  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。
• A convenient synthesis of carbohydrate derived furo/pyrano[2,3-b]pyrans from 2-hydroxymethyl glycals
  作者：Sudharani Chalapala、Ramakrishna Bandi、Venkatesh Bhumireddy Chinnachennaiahgari、Ramu Sridhar Perali

  DOI：10.1016/j.tet.2017.05.069

  日期：2017.7

  An efficient method for the stereoselective synthesis of various linearly fused bicyclic acetals using 2-hydroxymethyl glycals, involving Ferrier type rearrangement and ring-closing metathesis as the key steps, is revealed. The methodology was shown to be very general by applying it to various sugar substrates which lead to the formation of various bicyclic furo/pyrano[2,3-b]pyran ring systems.

  揭示了一种有效的方法，该方法使用2-羟甲基缩醛，以Ferer型重排和闭环复分解为关键步骤，立体选择性地合成了各种线性稠合的双环缩醛。通过将其应用到各种糖底物上显示该方法是非常通用的，这导致形成各种双环呋喃/吡喃并[2,3- b ]吡喃环系统。
• 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.