3-(4,6-di-O-methyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-propene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 3-(4,6-di-O-methyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-propene
• 英文别名: 3,4,6-tri-O-acetyl-D-glucal；(2R,3S)-6-allyl-3-methoxy-2-(methoxymethyl)-3,6-dihydro-2H-pyran；(2R,3S,6R)-3,6-dihydro-3-methoxy-2-(methoxymethyl)-6-(2-propen-1-yl)-2H-pyran；(2R,3S,6R)-6-allyl-3-methoxy-2-(methoxymethyl)-3,6-dihydro-2H-pyran；(2R,3S,6R)-3-methoxy-2-(methoxymethyl)-6-prop-2-enyl-3,6-dihydro-2H-pyran
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: ZFACTHKWBICCGI-OUAUKWLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3,4,6-三-O-甲基-D-葡萄糖醛 在 三氟甲磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 3-(4,6-di-O-methyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-propene
  参考文献：
  名称：

  碳正离子的闪速电化学方法

  摘要：

  开发了一种新型流动电化学反应器，可在几秒钟内完成电解，能够快速生成短寿命碳阳离子，并在亲核试剂分解之前捕获反应。本方法适用于高反应性氧代碳鎓离子、N-酰基亚胺离子、糖基阳离子和费里尔阳离子。此外，成功地证明了使用流动反应器系统连续和快速合成药物前体。

  DOI：

  10.1002/anie.202116177

文献信息

• Direct one-pot conversion of acylated carbohydrates into their alkylated derivatives under heterogeneous reaction conditions using solid NaOH and a phase transfer catalyst
  作者：Soni Kamlesh Madhusudan、Geetanjali Agnihotri、Devendra S. Negi、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.03.007

  日期：2005.5

  A convenient one-pot protocol for the direct conversion of acyl-protected carbohydrates into their alkylated counterparts has been developed by using alkyl halides in the presence of solid sodium hydroxide and a phase transfer catalyst. These economically convenient, mild, two-phase reaction conditions allow the preparation of a variety of monosaccharide intermediates for use in the synthesis of complex

  通过在固体氢氧化钠和相转移催化剂存在下使用烷基卤，已经开发了一种方便的一锅法方案，用于将酰基保护的碳水化合物直接转化为其烷基化的对应物。这些经济上方便，温和的两相反应条件允许制备用于合成复杂寡糖的各种单糖中间体。
• Bi(OTf)₃as Novel and Efficient Catalyst for the Stereoselective Synthesis of<i>C</i>-Pseudoglycals
  作者：J. S. Yadav、B. V. S. Reddy、K. Srinivasa Reddy、L. Chandraiah、V. Sunitha

  DOI：10.1055/s-2004-831187

  日期：——

  d-Glycals undergo smoothly allylic rearrangement with allyltrimethylsilane and trimethylsilyl cyanide in the presence of catalytic amount of bismuth triflate to afford the corresponding 2,3-unsaturated allyl glycosides and glycosyl cyanides in excellent yields with high α-selectivity.

  d-甘露醇在催化量的三氟甲磺酸铋存在下，与烯丙基三甲基硅烷和三甲基硅基氰化物顺利进行烯丙位重排反应，高效地生成相应的2,3-不饱和烯丙基糖苷和糖基氰化物，产率优异且具有高度的α-选择性。
• Efficient carbon-Ferrier rearrangement on glycals mediated by ceric ammonium nitrate: Application to the synthesis of 2-deoxy-2-amino-<i>C</i>-glycoside
  作者：Alafia A Ansari、Y Suman Reddy、Yashwant D Vankar

  DOI：10.3762/bjoc.10.27

  日期：——

  A carbon-Ferrier rearrangement on glycals has been performed by using ceric ammonium nitrate to obtain products in moderate to good yields with high selectivity. The versatility of this method has been demonstrated by applying it to differently protected glycals and by employing several nucleophiles. The obtained C-allyl glycoside has been utilized for the synthesis of a orthogonally protected 2-a

  通过使用硝酸铈铵对糖类进行碳-费里叶重排，以高选择性获得中等至良好收率的产物。该方法的多功能性已通过将其应用于不同保护的糖类和使用几种亲核试剂来证明。获得的 C-烯丙基糖苷已用于合成正交保护的 2-氨基-2-脱氧-C-糖苷。
• Insight into the Ferrier Rearrangement by Combining Flash Chemistry and Superacids
  作者：Naresh Bhuma、Ludivine Lebedel、Hiroki Yamashita、Yutaka Shimizu、Zahra Abada、Ana Ardá、Jérôme Désiré、Bastien Michelet、Agnès Martin‐Mingot、Ali Abou‐Hassan、Masahiro Takumi、Jérôme Marrot、Jesús Jiménez‐Barbero、Aiichiro Nagaki、Yves Blériot、Sébastien Thibaudeau

  DOI：10.1002/anie.202010175

  日期：2021.1.25

  to observe this ionic species, its extended lifetime in superacid solutions allowed its characterization by NMR‐based structural analysis supported by DFT calculations. This allyloxycarbenium ion was further exploited in the Ferrier rearrangement to afford unsaturated nitrogen‐containing C‐aryl glycosides and C‐alkyl glycosides under superacid and flow conditions, respectively.

  费里尔（Ferrier）于1962年报道，将糖类转化为2,3-不饱和糖基衍生物的过程涉及α，β不饱和糖基阳离子，这是一种尚难于观察的离子性离子。在本文中，虽然TfOH和流动条件的组合未能观察到该离子种类，但其在超强酸溶液中的延长寿命使其能够通过DFT计算支持的基于NMR的结构分析进行表征。该烯丙基氧碳鎓离子进一步在Ferrier重排中得到利用，分别在过酸和流动条件下提供了不饱和的含氮C-芳基糖苷和C-烷基糖苷。
• Flash Electrochemical Approach to Carbocations
  作者：Masahiro Takumi、Hodaka Sakaue、Aiichiro Nagaki

  DOI：10.1002/anie.202116177

  日期：2022.3

  electrochemical reactor that accomplishes electrolysis within a few seconds was developed, enabling flash generation of short-lived carbocations and trapping reaction with nucleophiles before they decompose. The present methodology was applied to highly reactive oxocarbenium ions, N-acyliminium ions, glycosyl cations, and the Ferrier cations. Moreover, continuous and flash synthesis of a pharmaceutical

  开发了一种新型流动电化学反应器，可在几秒钟内完成电解，能够快速生成短寿命碳阳离子，并在亲核试剂分解之前捕获反应。本方法适用于高反应性氧代碳鎓离子、N-酰基亚胺离子、糖基阳离子和费里尔阳离子。此外，成功地证明了使用流动反应器系统连续和快速合成药物前体。