ethyl 4,6-di-O-acetyl-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside | 3323-72-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl 4,6-di-O-acetyl-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
• 英文别名: [(2R,3S,6R)-3-acetyloxy-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 3323-72-6；56196-39-5；61826-47-9；63976-48-7；69055-68-1；78148-04-6
• 化学式: C₁₂H₁₈O₆
• 分子量: 258.271
• InChiKey: OSPOBRCWZOKNRC-QJPTWQEYSA-N

物化性质

• 熔点：
  77-79 °C(lit.)
• 溶解度：
  二氯甲烷：0.1 g/mL，澄清

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 安全说明：
  S22,S24/25
• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  ethyl 4,6-di-O-acetyl-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside 在 咪唑 、 sodium methylate 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 72.75h， 生成 ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-β-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds

  摘要：

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.

  DOI：

  10.1021/jo961881o
• 作为产物：
  描述：

  ethyl 3,4,6-tri-O-acetyl-2-acetoxymercury-2-deoxy-β-D-glucopyranoside 在 sodium iodide 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以85%的产率得到ethyl 4,6-di-O-acetyl-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Baer, Hans H.; Hanna, Zaher S., Canadian Journal of Chemistry, 1981, vol. 59, p. 889 - 906

  摘要：

  DOI：

文献信息

• A Highly Efficient Magnetic Iron(III) Nanocatalyst for Ferrier Rearrangements
  作者：Youxian Dong、Zekun Ding、Hong Guo、Le Zhou、Nan Jiang、Heshan Chen、Saifeng Qiu、Xiaoxia Xu、Jianbo Zhang

  DOI：10.1055/s-0037-1611855

  日期：2019.7

  A novel and highly efficient magnetic Fe3O4@C@Fe(III) core–shell catalyst, in which the carbon shell was prepared from lotus leaf, was fabricated. This nanocatalyst was successfully applied in the synthesis of a series of 2,3-unsaturated O-glycosides in excellent yields and with high selectivity, especially in the case of 2-halo O-glycosides, which differ in reactivity from nonsubstituted O-glycosides

  制备了一种新型高效的磁性 Fe3O4@C@Fe(III) 核壳催化剂，其中碳壳由荷叶制备。该纳米催化剂成功地应用于合成一系列 2,3-不饱和 O-糖苷，收率高，选择性高，特别是在反应性与未取代 O-糖苷不同的 2-卤代 O-糖苷的情况下，但以前几乎没有探索过。此外，通过施加外部磁力，催化剂可以很容易地从反应中分离出来，并且至少重复使用五次，而不会显着降低产品的产率。此外，该反应在克级规模上很容易进行，这为未来的应用提供了广阔的前景。
• Ferrier Rearrangement Catalyzed by HClO₄-SiO₂: Synthesis of 2,3-Unsaturated Glycopyranosides
  作者：Anup Kumar Misra、Pallavi Tiwari、Geetanjali Agnihotri

  DOI：10.1055/s-2004-837297

  日期：——

  Alkyl 2,3-unsaturated glycopyranosides have been prepared by the Ferrier rearrangement of acetyl protected glycals catalyzed by HClO 4 -SiO 2 . Operational simplicity, use of economically convenient catalyst, mild reaction conditions, high yields, short reaction times are the key features of this protocol.

  已通过 HClO 4 -SiO 2 催化乙酰保护糖基的 Ferrier 重排制备烷基 2,3-不饱和吡喃糖苷。操作简单、使用经济上方便的催化剂、温和的反应条件、高收率、短反应时间是该协议的主要特点。
• Magnetic Core-Shell Fe3O4@C-SO3H as an Efficient and Renewable ‘Green Catalyst’ for the Synthesis of O-2,3-Unsaturated Glycopyranosides
  作者：Jianbo Zhang、Guosheng Sun、Saifeng Qiu、Zekun Ding、Heshan Chen、Jiafen Zhou、Zhongfu Wang

  DOI：10.1055/s-0036-1588891

  日期：——

  rearrangement. The donors include 3,4,6-tri-O-acetyl- d -glucal and 3,4-di-O-acetyl- l -rhamnal. The acceptors consist of primary alcohols, secondary alcohols, tert-butanol, unsaturated alcohols, halogenated alcohol, sterol, sugars, and phenols. O-2,3-Unsaturated glycosides were obtained rapidly ( 5:1 to 19:1). Moreover, the catalyst can be easily separated from the reaction with an external magnetic force

  研究了一种磁性核壳固体酸催化剂 Fe3O4@C-SO3H，用于通过费里叶重排合成 O-2,3-不饱和糖苷。供体包括3,4,6-三-O-乙酰-d-葡糖醛和3,4-二-O-乙酰-1-鼠李醛。受体由伯醇、仲醇、叔丁醇、不饱和醇、卤代醇、甾醇、糖和酚组成。快速获得 O-2,3-不饱和糖苷（5:1 至 19:1）。此外，该催化剂可以很容易地通过外部磁力从反应中分离出来并重复使用至少 5 次，每次循环后产物的产率没有任何显着下降，表明它是一种很有前途的 2,3-不饱和绿色催化剂。糖苷合成。
• A Facile H2SO4/4 Å Molecular Sieves Catalyzed Synthesis of 2,3-Unsaturated O-Glycosides via Ferrier-Type Rearrangement
  作者：Jianbo Zhang、Jiafen Zhou、Bo Zhang、Guofang Yang、Xuan Chen、Qingbing Wang、Zhongfu Wang、Jie Tang

  DOI：10.1055/s-0029-1219539

  日期：2010.4

  A novel method for synthesizing 2,3-unsaturated glycosides has been developed using a metal-free catalytic system. This catalyst, sulfuric acid/4 Šmolecular sieves can catalyze the reaction of 3,4,6-tri-O-acetyl-d-glucals and a wide range of alcohols at room temperature, affording 2,3-unsaturated glycosides in good α-selectivity (α/β > 6:1) via a Ferrier-type rearrangement.

  开发了一种无金属催化体系的新方法来合成2,3-不饱和糖苷。这种催化剂，即硫酸/4 Å分子筛，可以在室温下催化3,4,6-三-O-乙酰基-d-葡醛酸与多种醇的反应，通过Ferrier型重排得到高α-选择性（α/β > 6:1）的2,3-不饱和糖苷。
• [EN] TRANSACETALISATION PROCESS<br/>[FR] METHODE DE TRANSACETALISATION
  申请人：UNIV MONASH

  公开号：WO2005070911A1

  公开（公告）日：2005-08-04

  The invention relates to the resolution of racemic mixtures, and in particular to the separation of enantiomers of chiral alcohols utilising recyclable chiral auxiliaries. The present invention also relates to a process for preparing these recyclable chiral auxiliaries using an enantiomerically pure alcohol.

  这项发明涉及手性混合物的分离，特别是利用可回收手性辅助剂分离手性醇的对映体。本发明还涉及利用对映纯醇制备这些可回收手性辅助剂的方法。