2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-3,5-bis-(2,2-dimethyl-propionyloxy)-2-(2,2-dimethyl-propionyloxymethyl)-6-isopropenyloxy-tetrahydro-pyran-4-yl ester | 178403-58-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-3,5-bis-(2,2-dimethyl-propionyloxy)-2-(2,2-dimethyl-propionyloxymethyl)-6-isopropenyloxy-tetrahydro-pyran-4-yl ester
• 英文别名: [(2R,3R,4S,5R,6R)-3,4,5-tris(2,2-dimethylpropanoyloxy)-6-prop-1-en-2-yloxyoxan-2-yl]methyl 2,2-dimethylpropanoate
• CAS: 178403-58-2
• 化学式: C₂₉H₄₈O₁₀
• 分子量: 556.694
• InChiKey: KQAWNYOVAAVELG-ADAARDCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  39
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-3,5-bis-(2,2-dimethyl-propionyloxy)-2-(2,2-dimethyl-propionyloxymethyl)-6-isopropenyloxy-tetrahydro-pyran-4-yl ester 在 sodium methylate 作用下， 以 甲醇 为溶剂， 以82%的产率得到O-Isopropenyl α-D-glucopyranoside
  参考文献：
  名称：

  异丙烯基葡糖苷的水解机理。有关α端基异构体具有更高反应性的光谱证据。

  摘要：

  通过温度依赖性反应动力学，（1）H NMR，（18）O-和（2）溶剂对产物进行立体化学分析，研究了异丙烯基α-和β-吡喃葡萄糖苷（分别为1和2）的水解机理。 H标记实验，动力学溶剂氘同位素的作用以及一般酸催化的α值。化合物1和2是显示出仅通过裂解乙烯基醚而不是缩醛CO键进行水解的第一种乙烯基缩醛。尽管两种吡喃葡萄糖苷均经历不可逆的限速C质子化反应，但1的水解速度比2快约四倍，并且其活化焓比2的低5.8 kcal mol（-）（1），表明1在动力学上更高比2基本

  DOI：

  10.1021/jo9721249
• 作为产物：
  描述：

  (2S,3R,4S,5R,6R)-6-((新戊酰氧基)甲基)四氢-2H-吡喃-2,3,4,5-四 在 dimethyltitanocene 、 硫酸 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-3,5-bis-(2,2-dimethyl-propionyloxy)-2-(2,2-dimethyl-propionyloxymethyl)-6-isopropenyloxy-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  The Chemistry of Isopropenyl Glycopyranosides. Transglycosylations and Other Reactions

  摘要：

  Various anomerically pure isopropenyl alpha- and beta-glycopyranosides have been synthesized and shown to undergo synthetically useful transglycosylation reactions with a variety of primary and secondary carbohydrate alcohols. Although stable when stored, isopropenyl glycosides are readily activated as glycosyl donors by a variety of electrophiles, including N-iodosuccinimide/triflic acid, trimethylsilyl triflate, and triflic anhydride. Under conditions that retard formation of the glycosyl cation, the reactivity of isopropenyl glycosides is diverted away from transglycosylation and toward electrophilic addition across the vinyl ether double bond.

  DOI：

  10.1021/jo960190p

文献信息

• Hydrolysis of O-Isopropenyl Glucopyranosides Involves C-Protonation and Alkenyl Ether Cleavage and Exhibits a Kinetic Influence of Anomeric Configuration
  作者：H. Keith Chenault、Laura F. Chafin

  DOI：10.1021/jo00100a015

  日期：1994.10

  Hydrolysis of O-isopropenyl alpha-glucopyranoside occurs by C-protonation and alkenyl ether (not glycosidic) C-O bond cleavage and proceeds in 10 mM salicylate buffer, at pH 3.0 and 25 degrees C, 4.5 times faster than the similar hydrolysis of its beta anomer.
• The Chemistry of Isopropenyl Glycopyranosides. Transglycosylations and Other Reactions
  作者：H. Keith Chenault、Alfredo Castro、Laura F. Chafin、Jie Yang

  DOI：10.1021/jo960190p

  日期：1996.1.1

  Various anomerically pure isopropenyl alpha- and beta-glycopyranosides have been synthesized and shown to undergo synthetically useful transglycosylation reactions with a variety of primary and secondary carbohydrate alcohols. Although stable when stored, isopropenyl glycosides are readily activated as glycosyl donors by a variety of electrophiles, including N-iodosuccinimide/triflic acid, trimethylsilyl triflate, and triflic anhydride. Under conditions that retard formation of the glycosyl cation, the reactivity of isopropenyl glycosides is diverted away from transglycosylation and toward electrophilic addition across the vinyl ether double bond.
• Mechanism of Hydrolysis of Isopropenyl Glucopyranosides. Spectroscopic Evidence Concerning the Greater Reactivity of the α Anomer
  作者：H. Keith Chenault、Laura F. Chafin

  DOI：10.1021/jo9721249

  日期：1998.2.1

  shown to undergo hydrolysis exclusively by cleavage of the vinyl ether and not the acetal C-O bond. While both glucopyranosides undergo irreversible, rate-limiting C-protonation, 1 hydrolyzes approximately four times faster than 2 and has an enthalpy of activation that is 5.8 kcal mol(-)(1) lower than that of 2, suggesting that 1 is kinetically more basic than 2. Spectroscopic evidence indicates that conjugation

  通过温度依赖性反应动力学，（1）H NMR，（18）O-和（2）溶剂对产物进行立体化学分析，研究了异丙烯基α-和β-吡喃葡萄糖苷（分别为1和2）的水解机理。 H标记实验，动力学溶剂氘同位素的作用以及一般酸催化的α值。化合物1和2是显示出仅通过裂解乙烯基醚而不是缩醛CO键进行水解的第一种乙烯基缩醛。尽管两种吡喃葡萄糖苷均经历不可逆的限速C质子化反应，但1的水解速度比2快约四倍，并且其活化焓比2的低5.8 kcal mol（-）（1），表明1在动力学上更高比2基本