methyl (6Z,9Z,12Z,15S,16S)-15,16-dihydroxyoctadeca-6,9,12-trienoate | 479073-89-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (6Z,9Z,12Z,15S,16S)-15,16-dihydroxyoctadeca-6,9,12-trienoate
• CAS: 479073-89-7
• 化学式: C₁₉H₃₂O₄
• 分子量: 324.461
• InChiKey: JLVGJBVQKFLEFV-UHDIMCHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  23
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (6Z,9Z,12Z,15S,16S)-15,16-dihydroxyoctadeca-6,9,12-trienoate 在 lithium hydroxide 、 2,4,6-三氯苯甲酰氯 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 水 为溶剂， 反应 23.5h， 生成 aplyolide C
  参考文献：
  名称：

  First total synthesis of natural aplyolides C and E, ichthyotoxic macrolides isolated from the skin of the marine mollusc Aplysia depilans

  摘要：

  A convergent pathway is described for the synthesis of the marine macrolides aplyolides C 4 and E 5. The key fragment 8 was prepared stereo selectively by Sharpless asymmetric dihydroxylation of eneyne 13. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00575-x
• 作为产物：
  描述：

  1-溴-2-戊烯 在 Pd-BaSO₄ 喹啉 、 AD-mix-α 、 copper(l) iodide 、 甲基磺酰胺 、 四丁基氟化铵 、 氢气 、 caesium carbonate 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 46.5h， 生成 methyl (6Z,9Z,12Z,15S,16S)-15,16-dihydroxyoctadeca-6,9,12-trienoate
  参考文献：
  名称：

  First total synthesis of natural aplyolides C and E, ichthyotoxic macrolides isolated from the skin of the marine mollusc Aplysia depilans

  摘要：

  A convergent pathway is described for the synthesis of the marine macrolides aplyolides C 4 and E 5. The key fragment 8 was prepared stereo selectively by Sharpless asymmetric dihydroxylation of eneyne 13. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00575-x

文献信息

• On the influence of unsaturation on the macrolactonization of hydroxy fatty acids
  作者：Tonino Caruso、Carmen Donnamaria、Antonietta Artillo、Andrea Peluso、Aldo Spinella、Guglielmo Monaco

  DOI：10.1002/poc.1548

  日期：2009.10

  Regioselectivity and yields of Yamaguchi cyclization of (15S,16S)‐15,16‐dihydroxy‐otadecyl‐(6Z,9Z,12Z)‐trienoic acid and its saturated homologue have been compared at different temperatures and concentrations. For the unsaturated species the regioselectivity of cyclization depends on temperature to such an extent that the preferred regioisomer changes as the temperature changes, whereas for the saturated

  比较了在不同温度和浓度下（15S，16S）-15,16-二羟基十八烷基-（6Z，9Z，12Z）-三烯酸的山口环化的区域选择性和产率。对于不饱和物质，环化的区域选择性取决于温度，以至于优选的区域异构体随温度的变化而变化，而对于饱和的同系物，偶数环却始终是优选的。分子力学被用来解释这些发现。对于两种二羟基酸，有实验证据表明，与类似的单羟基内酯不同，两种单环区域异构体的产率是热力学控制的。不饱和一羟基酸的较高环化产率是根据构象预组织来解释的。
• Structure and Stereochemistry of Aplyolides A−E, Lactonized Dihydroxy Fatty Acids from the Skin of the Marine Mollusk <i>Aplysia depilans</i>
  作者：Aldo Spinella、Eva Zubía、Eugenia Martînez、Jesus Ortea、Guido Cimino

  DOI：10.1021/jo961805l

  日期：1997.8.1

  The opisthobranch Aplysia depilans contains in its dorsum five unprecedented C-16 and C-18 fatty acid lactones (2-6). Their structures were assigned on the bases of chemical and spectral methods. Lactone 2 is derived by cyclization of 15(S)-hydroxyhexadeca-4(2),7(2),10(2),13(Z)-tetraenoic acid. The absolute stereochemistry at C-15 was determined by Mosher's method after opening of the lactone ring. Two other lactones (3 and 5) result from the cyclization either at C-15 or C-16 of 15,16-dihydroxyoctadeca-9(Z),12(Z)-dienoic acid. They differ from the remaining pair (4 and 6) by the absence of an additional double bond at C-6. S absolute stereochemistry of the free carbinols in 3-6 was suggested by applying Mosher's method. The same absolute stereochemistry was assigned at all lactonized carbinol centers by isomerization of the lactones by ring opening and subsequent enzymatic cyclization.
• First total synthesis of natural aplyolides C and E, ichthyotoxic macrolides isolated from the skin of the marine mollusc Aplysia depilans
  作者：Tonino Caruso、Aldo Spinella

  DOI：10.1016/s0957-4166(02)00575-x

  日期：2002.10

  A convergent pathway is described for the synthesis of the marine macrolides aplyolides C 4 and E 5. The key fragment 8 was prepared stereo selectively by Sharpless asymmetric dihydroxylation of eneyne 13. (C) 2002 Elsevier Science Ltd. All rights reserved.