methyl (7S,14S)-(2E,4E,8E,10E)-8,14-dimethyl-7-hydroxy-2,4,8,10-hexadecatetraenoate | 170421-62-2

• 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 (7S,14S)-(2E,4E,8E,10E)-8,14-dimethyl-7-hydroxy-2,4,8,10-hexadecatetraenoate
• 英文别名: methyl (7S,14S)-8,14-dimethyl-4-hydroxyhexadecane-2E,4E,8E,10E-tetraenoate
• CAS: 170421-62-2
• 化学式: C₁₉H₃₀O₃
• 分子量: 306.445
• InChiKey: ASZBLQUWEIZHJP-PUBXNPNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.35
• 重原子数：
  22.0
• 可旋转键数：
  10.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  甲氧基-三氟甲基苯 、 methyl (7S,14S)-(2E,4E,8E,10E)-8,14-dimethyl-7-hydroxy-2,4,8,10-hexadecatetraenoate 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 以93%的产率得到
  参考文献：
  名称：

  Approaches towards the synthesis of papulacandin D: preparation and structural elucidation of the acyl side chain

  摘要：

  通过L-(+)-异亮氨酸的降解和全合成来确定papulacandin D的O-3′-酰基侧链的绝对立体化学。

  DOI：

  10.1039/c39950001145
• 作为产物：
  描述：

  methyl (7S,14S)-8,14-dimethyl-7-<(triethylsilyl)oxy>-2E,4E,8E,10E-hexadecanetetraenoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以98%的产率得到methyl (7S,14S)-(2E,4E,8E,10E)-8,14-dimethyl-7-hydroxy-2,4,8,10-hexadecatetraenoate
  参考文献：
  名称：

  Approaches towards the synthesis of papulacandin D: preparation and structural elucidation of the acyl side chain

  摘要：

  通过L-(+)-异亮氨酸的降解和全合成来确定papulacandin D的O-3′-酰基侧链的绝对立体化学。

  DOI：

  10.1039/c39950001145

文献信息

• Total synthesis of (+)-papulacandin D
  作者：Scott E. Denmark、Tetsuya Kobayashi、Christopher S. Regens

  DOI：10.1016/j.tet.2010.03.093

  日期：2010.6

  A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain. The C-arylglycopyranoside was prepared in 11 steps in a 30% overall yield from triacetoxyglucal. The fatty acid side-chain was also prepared in 11 steps in a 30% overall yield from geraniol. The key strategic transformations in the synthesis are: (1) a palladium-catalyzed, organosilanolate-based cross-coupling reaction of a dimethylglucal-silanol with an electron-rich and sterically hindered aromatic iodide and (2) a Lewis-base catalyzed, enantioselective allylation reaction of a dienal and allyltrichlorosilane. A critical element in the successful execution of the synthesis was the development of a suitable protecting group strategy that satisfied a number of stringent criteria. (C) 2010 Elsevier Ltd. All rights reserved.
• Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D
  作者：Anthony G. M. Barrett、Michael Peña、J. Adam Willardsen

  DOI：10.1021/jo951895e

  日期：1996.1.1

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).