5,6-Isopropylidene-2-keto-3-O-methyl-3-(2-but-3-enyl)-L-idono-γ-lactone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-Isopropylidene-2-keto-3-O-methyl-3-(2-but-3-enyl)-L-idono-γ-lactone
• 英文别名: (4R,5R)-4-but-3-en-2-yl-5-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methoxyoxolane-2,3-dione
• 化学式: C₁₄H₂₀O₆
• 分子量: 284.309
• InChiKey: BPKPZCHFVBPSDS-VBSWXGIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  5,6-O-isopropylidene-L-ascorbic acid 在 potassium carbonate 作用下， 以 四氢呋喃 、 二甲基亚砜 、 甲苯 为溶剂， 反应 6.67h， 生成 5,6-Isopropylidene-2-keto-3-O-methyl-3-(2-but-3-enyl)-L-idono-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

文献信息

• Chemistry of L-Ascorbic Acid: Regioselective and Stereocontrolled 2-C- and 3-C-Allylation via Thermal Claisen Rearrangement
  作者：Kandatege Wimalasena、Mathew P. D. Mahindaratne

  DOI：10.1021/jo00091a036

  日期：1994.6

  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.