para-methoxybenzyl 5-[(para-methoxybenzyl)oxy]pentanoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: para-methoxybenzyl 5-[(para-methoxybenzyl)oxy]pentanoate
• 英文别名: (4-Methoxyphenyl)methyl 5-[(4-methoxyphenyl)methoxy]pentanoate
• 化学式: C₂₁H₂₆O₅
• 分子量: 358.434
• InChiKey: LHOLZPSMKVBBPA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  para-methoxybenzyl 5-[(para-methoxybenzyl)oxy]pentanoate 、 三异丙基硅基乙炔 在 正丁基锂 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 12.75h， 以86%的产率得到7-[(para-methoxybenzyl)oxy]-1-triisopropylsilyl-hept-1-yn-3-one
  参考文献：
  名称：

  A concise route to the C3–C23 fragment of the macrolide palmerolide A

  摘要：

  A concise route to the C3-C23 part of the macrolide palmerolide A was developed. This part features the 7,10,11-trihydroxy sector containing the 8E-double bond as well as the 14,16-diene subunit. The stereocenter at C-7 originated from a Noyori reduction on alkynone 8. The substrate 16 containing an enyne was obtained via a Claisen rearrangement. The vicinal diol at C10,C11 was created by a Sharpless asymmetric dihydroxylation. After selective protecting group manipulations the propargylic alcohol was reduced with Red-Al to the E-alkylic alcohol 26. The conjugated diene in the fragment 40 resulted from a Stille cross-coupling reaction between the vinylstarmane derived from alkyne 30 and the vinyl iodide 39. The latter could conveniently be prepared by an aldol/Wittig strategy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.10.028
• 作为产物：
  描述：

  delta-戊内酯 、 4-甲氧基氯苄 在 氢氧化钾 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以89%的产率得到para-methoxybenzyl 5-[(para-methoxybenzyl)oxy]pentanoate
  参考文献：
  名称：

  A concise route to the C3–C23 fragment of the macrolide palmerolide A

  摘要：

  A concise route to the C3-C23 part of the macrolide palmerolide A was developed. This part features the 7,10,11-trihydroxy sector containing the 8E-double bond as well as the 14,16-diene subunit. The stereocenter at C-7 originated from a Noyori reduction on alkynone 8. The substrate 16 containing an enyne was obtained via a Claisen rearrangement. The vicinal diol at C10,C11 was created by a Sharpless asymmetric dihydroxylation. After selective protecting group manipulations the propargylic alcohol was reduced with Red-Al to the E-alkylic alcohol 26. The conjugated diene in the fragment 40 resulted from a Stille cross-coupling reaction between the vinylstarmane derived from alkyne 30 and the vinyl iodide 39. The latter could conveniently be prepared by an aldol/Wittig strategy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.10.028

文献信息

• Formal Total Synthesis of Palmerolide A
  作者：Martin Maier、Julia Jägel

  DOI：10.1055/s-0029-1216921

  日期：2009.9

  aldehyde 30 containing already the carbamate function. A HWE reaction produced the substrate for an intramolecular Heck coupling. In contrast to the Stille cyclization, the Heck cyclization produced only the desired 14E,16E-diene. Elaboration of the C-19 side chain led to the key lactone 38. asymmetric synthesis - dihydroxylations - Heck reaction - macrocycles - natural products

  描述了通向大内酯38的简洁途径，大内酯38是Nicolaou / Chen合成棕榈油内酯A的高级中间体。我们合成过程中的关键步骤包括炔烃的Noyori转移氢化，通过Claisen重排的扩链以及在烯炔上的ADH反应。在三键还原之后，选择性的甲硅烷基化作用用来区分二醇的羟基，这允许制备已经具有氨基甲酸酯功能的醛30。HWE反应产生用于分子内Heck偶联的底物。与Stille环化相反，Heck环化仅产生所需的14 E，16 E-二烯。精心制作的C-19侧链形成了关键的内酯38。 不对称合成-二羟基化-Heck反应-大环化合物-天然产物