ethyl (2E,4R,5R,7E)-5-[(tert-butyldimethylsilyl)oxy]-8-iodo-2,4,7-trimethyl-2,7-octadienoate | 952103-34-3

• 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: ethyl (2E,4R,5R,7E)-5-[(tert-butyldimethylsilyl)oxy]-8-iodo-2,4,7-trimethyl-2,7-octadienoate
• CAS: 952103-34-3
• 化学式: C₁₉H₃₅IO₃Si
• 分子量: 466.475
• InChiKey: HFODTZOVJQAMIL-SZCDAFSNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.25
• 重原子数：
  24.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl (2E,4R,5R,7E)-5-[(tert-butyldimethylsilyl)oxy]-8-iodo-2,4,7-trimethyl-2,7-octadienoate 在 4-二甲氨基吡啶 、 2-甲基-6-硝基苯甲酸酐 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.33h， 生成 ethyl (2E,4R,5R,7E)-8-iodo-5-[(2E,7S)-7-[(4-methoxyphenyl)methoxy]nona-2,8-dienoyl]oxy-2,4,7-trimethylocta-2,7-dienoate
  参考文献：
  名称：

  A synthetic approach to palmerolides via Negishi cross coupling. The challenge of the C15–C16 bond formation

  摘要：

  The esterification of fragment C1-C8 (2) with fragment C16-C23 (3) to give iodo derivative 4, followed by a Pd-catalysed coupling with a C9-C15 fragment (7 or 8), may provide a common precursor of most palmerolides. Ligands and reaction conditions were exhaustively examined to perform the C15-C16 bond formation via Negishi reaction. With simple models, pre-activated Pd-Xantphos and Pd-DPEphos complexes were the most efficient catalysts at RT. Zincation of the C9-C15 fragment (8) and cross coupling with 4 required 3 equiv of t-BuLi, 10 mol % of Pd-Xantphos and 60 degrees C. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.06.066
• 作为产物：
  描述：

  (E)-4-iodo-3-methylbut-3-enal 在 2,6-二甲基吡啶 、 四氯化钛 、 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 23.08h， 生成 ethyl (2E,4R,5R,7E)-5-[(tert-butyldimethylsilyl)oxy]-8-iodo-2,4,7-trimethyl-2,7-octadienoate
  参考文献：
  名称：

  A synthetic approach to palmerolides via Negishi cross coupling. The challenge of the C15–C16 bond formation

  摘要：

  The esterification of fragment C1-C8 (2) with fragment C16-C23 (3) to give iodo derivative 4, followed by a Pd-catalysed coupling with a C9-C15 fragment (7 or 8), may provide a common precursor of most palmerolides. Ligands and reaction conditions were exhaustively examined to perform the C15-C16 bond formation via Negishi reaction. With simple models, pre-activated Pd-Xantphos and Pd-DPEphos complexes were the most efficient catalysts at RT. Zincation of the C9-C15 fragment (8) and cross coupling with 4 required 3 equiv of t-BuLi, 10 mol % of Pd-Xantphos and 60 degrees C. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.06.066

文献信息

• Total Synthesis of the Originally Proposed and Revised Structures of Palmerolide A and Isomers Thereof
  作者：K. C. Nicolaou、Ya-Ping Sun、Ramakrishna Guduru、Biswadip Banerji、David Y.-K. Chen

  DOI：10.1021/ja710485n

  日期：2008.3.1

  Palmerolide A is a recently disclosed marine natural product possessing striking biological properties, including potent and selective activity against the melanoma cancer cell line UACC-62. The total syntheses of five palmerolide A stereoisomers, including the originally proposed (1) and the revised [ent-(19-epi-20-epi-1)] structures, have been accomplished. The highly convergent and flexible strategy

  Palmerolide A 是最近公开的一种海洋天然产物，具有惊人的生物学特性，包括针对黑色素瘤癌细胞系 UACC-62 的有效和选择性活性。五种palmerolide A立体异构体的全合成，包括最初提出的(1)和修改后的[ent-(19-epi-20-epi-1)]结构，已经完成。为这些综合开发的高度收敛和灵活的策略涉及构建关键构建块 2、19-epi-2、20-epi-2、ent-2、3、ent-3、4 和 ent-4，以及它们的组装和细化目标化合物。对于构建单元的结合，采用了Stille偶联反应、Yamaguchi酯化、Horner-Wadsworth-Emmons烯化和闭环复分解反应，后者对于palmerolide结构的大环的立体选择性形成至关重要。还研究了 Horner-Wadsworth-Emmons 烯化和 Yamaguchi 内酯化，并发现作为构建 Palmerolide
• Total Synthesis of the Originally Proposed and Revised Structures of Palmerolide A
  作者：K. C. Nicolaou、Ramakrishna Guduru、Ya-Ping Sun、Biswadip Banerji、David Y.-K. Chen

  DOI：10.1002/anie.200702243

  日期：2007.8.3