5,6-O-Isopropylidene-3-O-acetyl-2-O-trans-crotyl-L-ascorbic acid | 158598-30-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-O-Isopropylidene-3-O-acetyl-2-O-trans-crotyl-L-ascorbic acid
• 英文别名: [(2R)-4-[(E)-but-2-enoxy]-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-5-oxo-2H-furan-3-yl] acetate
• CAS: 158598-30-2
• 化学式: C₁₅H₂₀O₇
• 分子量: 312.32
• InChiKey: WHOBSYGXTQNHTL-PFDYWKIBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5,6-O-Isopropylidene-3-O-acetyl-2-O-trans-crotyl-L-ascorbic acid 以 甲苯 为溶剂， 生成 Acetic acid (2R,3R)-2-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-(1-methyl-allyl)-4,5-dioxo-tetrahydro-furan-3-yl ester 、 5,6-Isopropylidene-2-keto-3-O-acetyl-3-(2-but-2-enyl)-L-galactono-γ-lactone
  参考文献：
  名称：

  Chemistry of L-Ascorbic Acid: Regioselective and Stereocontrolled 2-C- and 3-C-Allylation via Thermal Claisen Rearrangement

  摘要：

  We report the convenient preparation of 3-O- and 2-O-allylated derivatives of 5,6-O-isopropylidene-L-ascorbic acid (1) with various allyl substituents in high yield and their quantitative thermal Claisen rearrangement to the corresponding 2-C- and 3-C-allylated derivatives with high regio- and stereoselectivity under relatively mild conditions. This reaction will now allow the synthesis of heretofore unknown 3-C-allylated derivatives of L-ascorbic acid in high yield. The high chiral induction at the substituents of the allylic carbon, especially in the case of the 3-O-methyl-2-O-crotyl derivative, is intriguing. This general method of preparation of 2-C- and 3-C-allylated derivatives of ascorbic acid may have important applications in synthetic organic and pharmaceutical chemistry.

  DOI：

  10.1021/jo00091a036
• 作为产物：
  描述：

  5,6-O-isopropylidene-L-ascorbic acid 在 吡啶 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 2.67h， 生成 5,6-O-Isopropylidene-3-O-acetyl-2-O-trans-crotyl-L-ascorbic acid
  参考文献：
  名称：

  Chemistry of L-Ascorbic Acid: Regioselective and Stereocontrolled 2-C- and 3-C-Allylation via Thermal Claisen Rearrangement

  摘要：

  We report the convenient preparation of 3-O- and 2-O-allylated derivatives of 5,6-O-isopropylidene-L-ascorbic acid (1) with various allyl substituents in high yield and their quantitative thermal Claisen rearrangement to the corresponding 2-C- and 3-C-allylated derivatives with high regio- and stereoselectivity under relatively mild conditions. This reaction will now allow the synthesis of heretofore unknown 3-C-allylated derivatives of L-ascorbic acid in high yield. The high chiral induction at the substituents of the allylic carbon, especially in the case of the 3-O-methyl-2-O-crotyl derivative, is intriguing. This general method of preparation of 2-C- and 3-C-allylated derivatives of ascorbic acid may have important applications in synthetic organic and pharmaceutical chemistry.

  DOI：

  10.1021/jo00091a036

文献信息

• Rational Approach to Selective and Direct 2-<i>O</i>-Alkylation of 5,6-<i>O</i>-Isopropylidine-<scp>l</scp>-ascorbic Acid
  作者：Ayodele O. Olabisi、Kandatege Wimalasena

  DOI：10.1021/jo049319i

  日期：2004.10.1

  derivatives of l-ascorbic acid have been shown to possess antioxidant, antitumor, and immunostimulant activities. The antioxidant and redox properties of l-ascorbic acid are closely associated with the electron-rich 2,3-enediol moiety of the molecule, and therefore, selective functionalization of the 2- and 3-OH groups is essential for the detailed structure−activity studies. Reactions of 5- and 6-OH-protected

  1-抗坏血酸是一种广泛的自由基清除剂，广泛分布在需氧生物中，在保护细胞成分免受自由基和氧化剂的氧化损伤中起着核心作用。它也可作为生理还原剂，用于儿茶酚胺神经递质，酰胺化肽激素和胶原生物合成途径中的关键酶促转化。已显示1-抗坏血酸的简单衍生物具有抗氧化剂，抗肿瘤和免疫刺激活性。l的抗氧化和氧化还原特性-抗坏血酸与分子的富含电子的2,3-烯二醇部分紧密相关，因此，2-和3-OH基团的选择性官能化对于详细的结构活性研究至关重要。5-和6-OH-保护的抗坏血酸与亲电子试剂的反应由于C-3-OH的高亲核性，仅在温和的碱性条件下产生相应的3- O-烷基化产物。基于密度泛函理论（B3LYP）电子密度计算，我们设计了一种新颖的通用方法来对抗坏血酸的2-OH基团进行直接烷基化，具有完全的区域选择性和化学选择性。我们还对两个互补的2 - O-乙酰-3- O进行了完整的光谱分析-烷基-和2 - O-烷基-3-
• A Convenient Entry to C2- and C3-Substituted Gulono-γ-lactone Derivatives from <scp>l</scp>-Ascorbic Acid
  作者：Ayodele O. Olabisi、Mathew P. D. Mahindaratne、Kandatege Wimalasena

  DOI：10.1021/jo0508550

  日期：2005.8.1

  method to obtain unknown chiral C2- and C3-functionalized aldono-1,4-lactone derivatives starting from l-ascorbic acid, which would be valuable in the synthesis of derivatives of various pharmacologically active agents for structure−activity studies, is described. The practicality of this approach is demonstrated by the synthesis of a series of 5,6-O-isopropylidene-2-allyl-3-keto-l-galactono-γ-lactone

  描述了一种方便的方法，该方法从1-抗坏血酸开始获得未知的手性C2-和C3官能化的aldono-1,4-内酯衍生物，这对合成各种用于结构活性研究的药理活性剂具有价值的方法。该方法的实用性通过合成一系列的5，6 - O-异亚丙基-2-烯丙基-3-酮基-1-半乳糖-γ-内酯和5，6 - O-异亚丙基-3-烯丙基-来证明。 2-酮升使用相应的3-的热克莱森重排-galactono-γ内酯衍生物ø -和2- ö 5,6-的烯丙基衍生物ö异亚丙基升-抗坏血酸，然后立体定向还原为相应的醇。合成步骤被证明是有效的和对映体特异性的，并且它们以高收率进行。