methyl (5S,6R)-5,6-bis(tert-butyldimethylsilyloxy)oct-7-enoate | 960510-79-6

• 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 (5S,6R)-5,6-bis(tert-butyldimethylsilyloxy)oct-7-enoate
• 英文别名: (5S,6R)-methyl 5,6-bis((tert-butyldimethylsilyl)oxy)oct-7-enoate；Methyl (5S,6R)-5,6-bis((tert-butyldimethylsilyl)oxy)oct-7-enoate；methyl (5S,6R)-5,6-bis[[tert-butyl(dimethyl)silyl]oxy]oct-7-enoate
• CAS: 960510-79-6
• 化学式: C₂₁H₄₄O₄Si₂
• 分子量: 416.749
• InChiKey: QYBXZOVETTYPRB-MSOLQXFVSA-N

物化性质

• 沸点：
  401.0±45.0 °C(Predicted)
• 密度：
  0.908±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  27
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (5S,6R)-5,6-bis(tert-butyldimethylsilyloxy)oct-7-enoate 在 Selectfluor 作用下， 以 乙腈 为溶剂， 反应 0.17h， 以97%的产率得到(5S,6R)-5,6-dhydroxyoct-7-enoic acid methyl ester
  参考文献：
  名称：

  Selectfluor对硅醚的新型，化学选择性和高效微波辅助脱保护

  摘要：

  报道了一种新型的微波辅助，化学选择性和高效的方法，用于Selectfluor催化的甲硅烷基醚（脂族和芳族）裂解。在芳基甲硅烷基醚的存在下，可以高收率化学选择裂解各种TBS，TIPS和TBDPS保护的烷基甲硅烷基醚。在这些反应条件下，还可以实现酚TBS醚而不是TIPS或TBDPS保护的酚醚的化学选择性脱保护，以及甲硅烷基酯的脱保护。另外，观察到在醇溶剂中苄基羟基的醚交换和醚化。

  DOI：

  10.1021/jo802494t
• 作为产物：
  描述：

  在 potassium tert-butylate 、 水 、 戴斯-马丁氧化剂 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 21.5h， 生成 methyl (5S,6R)-5,6-bis(tert-butyldimethylsilyloxy)oct-7-enoate
  参考文献：
  名称：

  Synthesis of Bifunctional Lipoxin‐Derived Enzyme‐Triggered CO‐Releasing Molecules (LipET‐CORMs)

  摘要：

  AbstractIn an attempt to develop new anti‐inflammatory agents which act by co‐release of carbon monoxide (CO) and a specialized pro‐resolving mediator, we designed conjugates of a lipoxin A4 analogue and an acyloxycyclohexadiene‐Fe(CO)3 complex as an esterase‐triggered CO‐releasing molecule (ET‐CORM). After adjustment of the protecting group strategy, two of such compounds were successfully prepared by total synthesis (12 steps; 4–5 % overall yield) starting from deoxy‐d‐ribose and exploiting a Wittig olefination and an intermolecular Heck reaction as key C−C bond‐forming steps. A crucial late reduction of an aryl‐ketone moiety in the presence of a highly sensitive dienol ester functionality was achieved with BH3‐SMe2 in the presence of catalytic amounts of NaBH4. Both target compounds were dose‐dependently toxic towards cultured human umbilical vein endothelial cells (HUVEC), with LipET‐CORM 1‐A being slightly more toxic. While induction of heme oxygenase 1 (HO‐1) in HUVEC was observed for both compounds, they did not inhibit TNF‐α‐mediated VCAM‐1 expression in these cells. In M2 polarized macrophages HO‐1 expression was more pronounced as compared to M1 polarized macrophages. In both types of macrophages HO‐1 expression was downregulated by lipopolysaccharide, but only in M2 macrophages HO‐1 expression was rescued by LipET‐CORM. 15‐Lipoxygenase (15‐LO) was only expressed in M2 macrophages and was not influenced by LipET‐CORM. Collectively our data demonstrate that LipET‐CORMs induce HO‐1 expression in endothelial cells and M2 polarized macrophages. The role of the intra‐cellular released lipoxin A4 in resolution of inflammation, however, remains to be assessed.

  DOI：

  10.1002/ejoc.202201424

文献信息

• The chemoselective and efficient deprotection of silyl ethers using trimethylsilyl bromide
  作者：Syed Tasadaque A. Shah、Patrick J. Guiry

  DOI：10.1039/b803949f

  日期：——

  An efficient and chemoselective cleavage of silyl ethers (primary, secondary and aromatic) by using catalytic quantities of trimethylsilyl bromide (TMSBr) in methanol is reported. A wide range of alkyl silyl ethers such as TBS, TIPS, and TBDPS can be chemoselectively cleaved in high yield in the presence of aryl silyl ethers. The deprotection of silyl esters was also achieved employing catalytic quantities

  据报道，通过在甲醇中使用催化量的三甲基甲硅烷基溴化物（TMSBr），可以高效，化学选择性地裂解甲硅烷基醚（伯，仲和芳族化合物）。在芳基甲硅烷基醚的存在下，可以高收率化学选择裂解多种烷基甲硅烷基醚，例如TBS，TIPS和TBDPS。还使用催化量的TMSBr实现甲硅烷基酯的脱保护。
• ZrCl₄ as an Efficient Catalyst for a Novel One-Pot Protection/Deprotection Synthetic Methodology
  作者：Surendra Singh、Colm D. Duffy、Syed Tasadaque A. Shah、Patrick J. Guiry

  DOI：10.1021/jo800932t

  日期：2008.8.1

  found to be an efficient catalyst for the one-pot esterification and deprotection of (5S,6R)-5,6-diacetoxyoct-7-enoic acid in good yields (44−62%) with a lactone formed as a minor byproduct. ZrCl4 (10−20 mol %) was also sufficient to deprotect 1,3-dioxalane, bis-TBDMS ethers, and diacetate functional groups in excellent yields of up to 93%. ZrCl4 (1−10 mol %) also promoted diol protection as the acetonide

  发现催化量的ZrCl 4（20 mol％）是一种有效的催化剂，用于以高收率一锅法酯化和（5 S，6 R）-5,6-二乙酰氧基辛-7-烯酸脱保护（44 -62％），形成内酯为次要副产物。ZrCl 4（10-20 mol％）也足以以高达93％的优异收率对1,3-二氧杂戊环，bis-TBDMS醚和二乙酸酯官能团进行脱保护。ZrCl 4（1-10 mol％）还以90％的收率促进了作为丙酮化物的二醇保护作用，并充当了一系列酯的酯交换催化剂。
• Aromatic Lipoxin A₄ and Lipoxin B₄ Analogues Display Potent Biological Activities
  作者：Timothy P. O'Sullivan、Karl S. A. Vallin、Syed Tasadaque Ali Shah、Jérôme Fakhry、Paola Maderna、Michael Scannell、Andre L. F. Sampaio、Mauro Perretti、Catherine Godson、Patrick J. Guiry

  DOI：10.1021/jm060270d

  日期：2007.11.1

  aromatic LXA4 and LXB4 analogues by employing Sharpless epoxidation, Pd-mediated Heck coupling, and diastereoselective reduction as the key transformations. Subsequent biological testing has shown that these analogues display potent biological activities. Phagocytic clearance of apoptotic leukocytes plays a critical role in the resolution of inflammation. Both LXA4 analogues (1R)-3a and (1S)-3a were

  脂蛋白是一组通常通过跨细胞脂氧合酶活性形成的生物活性类花生酸。在多种炎症条件下均已检测到脂氧合蛋白A4（LXA4）和脂氧合蛋白B4（LXB4）的生物合成。天然脂毒素LXA4和LXB4表现出有效的抗炎和分解生物作用。然而，它们的治疗潜力受到PG脱氢酶介导的氧化和还原作用的快速代谢失活的影响。在这里，我们报告通过采用Sharpless环氧化，Pd介导的Heck偶联和非对映选择性还原作为关键转化，对芳香族LXA4和LXB4类似物进行立体选择性合成。随后的生物学测试表明，这些类似物显示出强大的生物学活性。凋亡性白细胞的吞噬清除在炎症消退中起关键作用。发现LXA4类似物（1R）-3a和（1S）-3a均能刺激巨噬细胞吞噬凋亡性多形核白细胞（PMN）的吞噬作用显着增加，其功效与天然LXA4相当，尽管效力更高，而LXB4类似物还刺激吞噬作用，在10-11 M时观察到最大作用。LX刺激的吞噬作用与肌动蛋白细
• Synthesis and Biological Evaluation of Pyridine-Containing Lipoxin A₄Analogues
  作者：Colm D. Duffy、Paola Maderna、Ciara McCarthy、Christine E. Loscher、Catherine Godson、Patrick J. Guiry

  DOI：10.1002/cmdc.200900533

  日期：2010.4.6

  A short and efficient synthesis of new pyridine‐containing lipoxin A4 analogues was developed. These analogues induce phagocytosis of apoptotic polymorphonuclear leukocytes and display anti‐ inflammatory characteristics by suppressing pro‐inflammatory cytokine production by macrophages.

  快速有效地合成了新的含吡啶脂质新A 4类似物。这些类似物通过抑制巨噬细胞促炎细胞因子的产生，诱导细胞凋亡的多形核白细胞的吞噬作用并表现出抗炎特性。
• [EN] HETEROCYCLIC LIPOXIN ANALOGS AND USES THEREOF<br/>[FR] ANALOGUES DE LIPXON HÉTÉROCYCLIQUES ET LEURS UTILISATIONS
  申请人：UNIV DUBLIN

  公开号：WO2018033642A9

  公开（公告）日：2018-10-18