2(S)-methyl-3(R)-carboxy-4(S)-hydroxy-18-oxononadecan-1-4-olide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 2(S)-methyl-3(R)-carboxy-4(S)-hydroxy-18-oxononadecan-1-4-olide
• 英文别名: (-)-dihydropertusaric acid；(-)₅₈₉-Dihydropertusaric acid；(2S,3R,4S)-4-methyl-5-oxo-2-(14-oxopentadecyl)oxolane-3-carboxylic acid
• 化学式: C₂₁H₃₆O₅
• 分子量: 368.514
• InChiKey: SPGPUDJMXMJNCU-GBESFXJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  80.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2(S)-methyl-3(R)-carboxy-4(S)-hydroxy-18-oxononadecan-1-4-olide 在 三氟化硼乙醚 作用下， 以 乙醚 、 溶剂黄146 为溶剂， 反应 24.17h， 生成 (-)₅₈₉-18,18-(Ethylenedithio)-3-(methoxycarbonyl)-2-methyl-4-nonadecanolide
  参考文献：
  名称：

  (-)-Allo-pertusaric acid 和 (-)-dihydropertusaric acid 来自地衣 Pertusaria albescens

  摘要：

  摘要 已经通过光谱和化学方法阐明了来自白百合地衣的两种γ-内酯羧酸、(-)-异位百日咳酸和(-)二氢百日咳酸的结构。已从 P. ophthalmiza 中分离出蒲公英和长链脂肪醇和脂肪酸的混合物。

  DOI：

  10.1016/s0031-9422(00)85500-4
• 作为产物：
  描述：

  15-Bromo-2-pentadecanone 在 氯化锆(IV) 盐酸 、 N-溴代丁二酰亚胺(NBS) 、 三氟化硼乙醚 、 碘 、 对甲苯磺酸 、 magnesium 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 79.59h， 生成 2(S)-methyl-3(R)-carboxy-4(S)-hydroxy-18-oxononadecan-1-4-olide
  参考文献：
  名称：

  Ring-opening aldol-type reaction of 2,2-dialkoxycyclopropanecarboxylic esters with carbonyl compounds. 3. The diastereoselective synthesis of 2,3,4-trisubstituted .gamma.-lactones

  摘要：

  The Lewis acid-promoted reaction of 3-alkyl-2,2-dialkoxycyclopropanecarboxylic esters 1d-h with aldehydes to give 2,3,4-trisubstituted gamma-lactones was investigated. The diastereoselectivity of this reaction is highly dependent on the catalyst employed. Thus while the ZrCl4-promoted reaction gave (2alpha,3alpha,4beta)-trisubstituted gamma-lactones in good yields with excellent selectivity, the SnBr4-promoted reaction was moderately selective for (2alpha,3alpha,4alpha)-trisubstituted gamma-lactones. The present reaction was applied to the synthesis of (+)589- and (-)589-dihydropertusaric acid (26). Comparison of the spectroscopic and physical data of synthetic 26 with those of a 4-alkyl-3-carboxy-2-methyl gamma-lactone isolated from the lichen Pertusaria albescens revealed that the relative stereochemistry of the natural gamma-lactone was not (2beta,3beta,4alpha), as reported by Huneck and his co-workers, but rather (2beta,3alpha,4alpha); that is, the natural gamma-lactone was not (-)589-dihydropertusaric acid (26), but (-)589-pertusarinic acid (27).

  DOI：

  10.1021/jo00071a036

文献信息

• Ring-opening aldol-type reaction of 2,2-dialkoxycyclopropanecarboxylic esters with carbonyl compounds. 3. The diastereoselective synthesis of 2,3,4-trisubstituted .gamma.-lactones
  作者：Shigeru Shimada、Yukihiko Hashimoto、Kazuhiko Saigo

  DOI：10.1021/jo00071a036

  日期：1993.9

  The Lewis acid-promoted reaction of 3-alkyl-2,2-dialkoxycyclopropanecarboxylic esters 1d-h with aldehydes to give 2,3,4-trisubstituted gamma-lactones was investigated. The diastereoselectivity of this reaction is highly dependent on the catalyst employed. Thus while the ZrCl4-promoted reaction gave (2alpha,3alpha,4beta)-trisubstituted gamma-lactones in good yields with excellent selectivity, the SnBr4-promoted reaction was moderately selective for (2alpha,3alpha,4alpha)-trisubstituted gamma-lactones. The present reaction was applied to the synthesis of (+)589- and (-)589-dihydropertusaric acid (26). Comparison of the spectroscopic and physical data of synthetic 26 with those of a 4-alkyl-3-carboxy-2-methyl gamma-lactone isolated from the lichen Pertusaria albescens revealed that the relative stereochemistry of the natural gamma-lactone was not (2beta,3beta,4alpha), as reported by Huneck and his co-workers, but rather (2beta,3alpha,4alpha); that is, the natural gamma-lactone was not (-)589-dihydropertusaric acid (26), but (-)589-pertusarinic acid (27).
• (−)-Allo-pertusaric acid and (−)-dihydropertusaric acid from the lichen Pertusaria albescens
  作者：Siegfried Huneck、Tor Tønsberg、Ferdinand Bohlmann

  DOI：10.1016/s0031-9422(00)85500-4

  日期：1986.1

  Abstract The structures of two γ-lactone carboxylic acids from the lichen Pertusaria albescens , (−)-allo-pertusaric acid and (−)dihydropertusaric acid, have been elucidated by spectroscopic and chemical methods. From P. ophthalmiza , taraxerone and a mixture of long chain aliphatic alcohols and fatty acids have been isolated.

  摘要 已经通过光谱和化学方法阐明了来自白百合地衣的两种γ-内酯羧酸、(-)-异位百日咳酸和(-)二氢百日咳酸的结构。已从 P. ophthalmiza 中分离出蒲公英和长链脂肪醇和脂肪酸的混合物。